US5972527A - Transparent electrically conductive layer, electrically conductive transparent substrate and electrically conductive material - Google Patents

Transparent electrically conductive layer, electrically conductive transparent substrate and electrically conductive material Download PDF

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US5972527A
US5972527A US08/446,584 US44658495A US5972527A US 5972527 A US5972527 A US 5972527A US 44658495 A US44658495 A US 44658495A US 5972527 A US5972527 A US 5972527A
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electrically conductive
transparent
conductive layer
atomic ratio
indium
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Akira Kaijou
Masashi Ohyama
Masatoshi Shibata
Kazuyoshi Inoue
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Idemitsu Kosan Co Ltd
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Assigned to IDEMITSU KOSAN CO., LTD. reassignment IDEMITSU KOSAN CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INOUE, KAZUYOSHI, KAIJOU, AKIRA, OHYAMA, MASASHI, SHIBATA, MASATOSHI
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31609—Particulate metal or metal compound-containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31942—Of aldehyde or ketone condensation product

Definitions

  • the present invention relates to a transparent electrically conductive layer, an electrically conductive substrate formed of the transparent electrically conductive layer, and an electrically conductive material suitable as a material for obtaining the above transparent electrically conductive layer.
  • a liquid crystal display apparatus can be decreased in weight and thickness and actuated at a low voltage, and it is therefore actively introduced to office automation machines and equipment such as a personal computer, a word processor, etc. And, a liquid crystal display apparatus having the above advantages is inevitably designed toward a larger screen, an increase in the number of picture element pixels and higher preciseness, and there is desired a high-quality liquid crystal display apparatus free of display defects.
  • a liquid crystal display device has a sandwich structure in which a liquid crystal is sandwiched between mutually opposing two transparent electrodes, and the transparent. electrodes constitute one important element for obtaining a high-quality liquid crystal display device.
  • the transparent electrode is fabricated, for example, by patterning a transparent electrically conductive layer formed on a transparent glass substrate, to a predetermined form by photolithography. In recent years, for further decreasing the weight of a display apparatus, it is under way to make attempts to substitute polymer films for the transparent glass substrate.
  • an ITO electrode is the mainstream as a transparent electrode.
  • An ITO layer which constitutes the base of the ITO electrode is formed by a sputtering method using ITO as a sputtering target. It is because an ITO layer not only has high transparency and low resistance but also has excellent etching properties (etching rate) and excellent adhesion to a substrate that a large number of ITO electrodes are used.
  • the substrate temperature is set at 200-300° C. for obtaining an ITO layer having a low electric resistance and high transparency.
  • the ITO layer is crystallized.
  • the etching properties are good, but cannot be said to be excellent.
  • a polymer film or a resin substrate is used as a substrate, it is difficult to set the substrate temperature at 200-300° C., and it is therefore difficult to form an ITO layer having a low electric resistance and high transparency.
  • the ITO layer can be improved in the etching properties by preparing the ITO layer as an amorphous one (see U.S. Pat. No.
  • an ITO electrode obtained by shaping this ITO layer into a predetermined form has a problem in that the electrical conductivity and the light transmittance is liable to decrease with time while it is used. It markedly appears particularly in an amorphous ITO film that the resistance to moist heat is low so that the electrical conductivity and the light transmittance decrease with time.
  • the present invention has been made to provide a novel transparent electrically conductive layer which can replace the ITO layer having the above problems, and a novel electrically conductive transparent substrate which can replace an electrically conductive transparent substrate formed of the ITO layer. It is an object of the present invention to provide a transparent electrically conductive layer which has practically sufficient electrical conductivity and light transmittance and is excellent in resistance to moist heat and etching properties, and an electrically conductive transparent substrate formed of this transparent electrically conductive layer. It is another object of the present invention to provide an electrically conductive material suitable as a material for obtaining the above transparent electrically conductive layer.
  • the present inventors have made diligent studies expecting that a transparent electrically conductive layer having higher chemical stability than an ITO layer can be obtained by replacing Sn in ITO with other element.
  • an oxide which is an amorphous oxide containing indium (In) and zinc (Zn) as main cation elements and having a ratio between In and Zn in a specific range has practically sufficient electrical conductivity and light transmittance and is excellent in resistance to moist heat and etching properties, and the completion of the present invention has been arrived at.
  • a layer of indium oxide containing zinc oxide obtained by forming a coating on a substrate surface by dip-coating a coating solution containing indium nitrate and zinc nitrate in an atomic ratio of indium, In/(In+Zn), of 0.80, and subjecting the coating to predetermined heat treatment (see JP-B-5-6289).
  • the transparent electrically conductive layer of the present invention can be easily obtained as one having excellent electrical conductivity over the above layers (1) and (2) when formed by like methods (a sputtering method and an coating and thermal decomposition method).
  • the transparent electrically conductive layer of the present invention is characterized in that it is formed of an amorphous oxide containing indium (In) and zinc (Zn) as main cation elements, and that the atomic ratio of In, In/(In+Zn), is 0.50 to 0.90 (this transparent electrically conductive layer will be referred to as "transparent electrically conductive layer I" hereinafter).
  • Another transparent electrically conductive layer of the present invention is characterized in that it is a layer formed from an amorphous oxide containing, as main cation elements, at least ones of third elements having a valence of at least 3 (e.g., tin (Sn), aluminum (Al), antimony (Sb), gallium (Ga) and germanium (Ge)) in addition to In and Zn, that the atomic ratio of In, In/(In+Zn), is 0.50 to 0.90 and that the atomic ratio of the total amount of the above third elements (total third elements)/(In+Zn+total third elements) is 0.2 or less (this transparent electrically conductive film will be referred to as "transparent electrically conductive layer II" hereinafter).
  • transparent electrically conductive layer II this transparent electrically conductive film will be referred to as "transparent electrically conductive layer II" hereinafter).
  • the electrically conductive transparent substrate of the present invention is characterized in that the above transparent electrically conductive layer I or the above transparent electrically conductive layer II is formed on a transparent polymer substrate in the form of a film or a sheet directly or through at least a crosslinked resin layer (this electrically conductive transparent substrate will be referred to as "electrically conductive transparent film” hereinafter).
  • another electrically conductive transparent substrate of the present invention is characterized in that the above transparent electrically conductive layer I or the above transparent electrically conductive layer II is formed on a transparent glass substrate (this electrically conductive transparent substrate will be referred to as "electrically conductive transparent glass” hereinafter).
  • the electrically conductive material of the present invention includes the following electrically conductive materials a to b.
  • a. Material characterized in that it is a powder or a sintered body formed from an oxide containing indium (In) and zinc (Zn) as main cation elements and contains a hexagonal laminar compound of the general formula In 2 O 3 (ZnO) m (m 2-20) and that the atomic ratio of In, In/(In+Zn), is 0.1 to 0.9 (this electrically conductive material will be referred to as "electrically conductive material I" hereinafter).
  • the above electrically conductive material I may be substantially formed from at least one of hexagonal laminar compounds of the above general formula, or may be substantially formed from a material containing crystalline or amorphous In 2 O 3 and/or ZnO in addition to at least one of hexagonal laminar compounds of the above formula. b.
  • third elements having a valence of at least 3 (e.g., tin (Sn), aluminum (Al), antimony
  • the above electrically conductive material II may be substantially formed from at least one of the above compounds, and may be formed from a material containing crystalline or amorphous In 2 O 3 and/or ZnO in addition to at least one of the above compound.
  • FIG. 1 is a graph showing the result of measurement of a transparent electrically conductive layer I obtained in Example 1 (calcining temperature 500° C., firing temperature 500° C.) by XRD (X-ray diffraction).
  • this electrically conductive layer I of the present invention is formed from a amorphous oxide substantially containing In and Zn alone as main cation elements, and in this layer, the atomic ratio of In, In/(In+Zn), is 0.50 to 0.90. Oxygen in the above oxide may be partially missing in some cases. Further, this oxide includes oxides in all forms such as a mixture, a composition and a solid solution.
  • the atomic ratio, In/(In+Zn) is preferably 0.60 to 0.90.
  • the atomic ratio of In, In/(In+Zn) is more preferably 0.6 to 0.80 for a layer formed by a coating and thermal decomposition method, and 0.80 to 0.90 for a layer formed by the sputtering method.
  • the above atomic ratio is particularly preferably 0.60 to 0.75.
  • Crystalline layers have poor electrical conductivity as compared with amorphous layers even if these layers have the same composition.
  • the transparent electrically conductive layer I is therefore limited to amorphous layers. Further, when the atomic ratio, In/(In+Zn), of layers obtained by the coating and thermal decomposition method exceeds 0.80, the layers may show poor electrical conductivity in some cases.
  • the above oxide can be used as a transparent electrically conductive layer when formed as a thin layer.
  • the thickness of this layer can be properly selected depending upon use and a material of a substrate on which the transparent electrically conductive layer is formed, while it is generally in the range of 3 nm to 3,000 nm. When the layer thickness is less than 3 nm, the electrical conductivity is liable to be insufficient; when it exceeds 3,000 nm, the light transmittance is liable to decrease.
  • the transparent electrically conductive layer I of the above oxide is a transparent electrically conductive Layer having practically sufficient electrical conductivity and light transmittance and having excellent resistance to moist heat and etching properties.
  • the above transparent electrically conductive layer I can be produced by any one of various methods such as a coating and thermal decomposition method, a sputtering method and a CVD method.
  • a coating and thermal decomposition method For producing a layer at a low cost with easily controlling its composition, the production by a coating and thermal decomposition method is preferred.
  • the production by a sputtering method is preferred.
  • the transparent electrically conductive film I is produced by the coating and thermal decomposition method, there is prepared a coating solution in which an indium compound and a zinc compound are dissolved so that the atomic ratio of In, In/(In+Zn), is a predetermined value, the coating solution is applied to a predetermined substrate and fired at 300 to 650° C., and then the coating is reduction-treated to obtain the intended transparent electrically conductive layer I.
  • coating solution in which an indium compound and a zinc compound are dissolved so that the atomic ratio of In, In/(In+Zn), is a predetermined value refers to a coating solution in which an indium compound and a zinc compound are dissolved so that the atomic ratio of In, In/(In+Zn), of a layer as a final product is an intended value in the range of 0.50 to 0.90.
  • the above coating solution contains a solvent and a stabilizer for the solution in addition to the above indium compound and zinc compound.
  • the above indium compound include carboxylates such as indium acetate, inorganic indium compounds such as indium chloride, and indium alkoxides such as indium ethoxide and indium propoxide.
  • the zinc compound include carboxylates such as zinc acetate, inorganic zinc compounds such as zinc chloride, zinc fluoride and zinc iodide, and zinc alkoxides such as zinc methoxide, zinc ethoxide and zinc propoxide.
  • the above solvent can be selected from water, alcohols such as methanol, ethanol, isopropyl alcohol, 2-methoxyethanol and 2-ethoxyethanol and hydrocarbons such as toluene and benzene.
  • the above stabilizer for the solution can be selected from alaknolamines such as monoethanolamine, diethanolamine and triethanolamine. Of these, 2-methoxyethanol is preferred as a solvent, and monoethanolamine is preferred as a stabilizer.
  • the above coating solution can be prepared by mixing predetermined amounts of the indium compound, the zinc compound, the solvent and the stabilizer.
  • the order of mixing in this case is not specially limited.
  • the mixing may be a mixing with stirring with a stirrer according to a conventional method, and the mixing may be carried out under heat.
  • the time for the stirring is preferably 0.01 to 100 hours. When it is less than 0.01 hour, it is difficult to obtain a homogeneous transparent solution. When it exceeds 100 hours, it results in poor economic performance.
  • the time for the stirring is particularly preferably 0.1 to 10 hours.
  • the heating temperature is preferably up to 100° C. When it exceeds 100° C., the solvent evaporates to alter the solution concentration.
  • the concentration of the total content of In and Zn in the coating solution is preferably 0.01 to 10 mol %. When it is less than 0.01 mol %, the thickness of a coating formed by one coating operation is small, and it is required to carry out the coating operation many times, which results in poor economic performance. When the above concentration exceeds 10 mol %, a coating is nonuniform in thickness.
  • the concentration of the total content of I and Zn is particularly preferably 0.1 to 5 mol %.
  • the concentration of the stabilizer in the coating solution is preferably 0.01 to 50 ml %. When it is less than 0.01 mol %, it is difficult to dissolve the indium compound and the zinc compound in the solvent. On the other hand, when it exceeds 50 mol %, carbon formed by the decomposition of the stabilizer during the firing remains in the layer to decrease the electrical conductivity of the layer.
  • the concentration of the stabilizer is particularly preferably 0.1 to 10 mol %.
  • the coating solution prepared as described above is applied to a substrate, and then fired at 300 to 650° C.
  • the substrate may be selected from various substrates depending upon use.
  • the transparent substrate is selected from electrically insulating transparent materials such as soda-lime glass, lead glass, borosilicate glass, high silica glass, alkali-free glass, alkali glass, quartz glass and a highly heat-resistant transparent polymer.
  • the substrate may have an undercoating layer. Specific examples of the undercoating layer include thin films of ZnO, SiO 2 and TiO 2 .
  • the method for the application of the coating solution to the substrate is not specially limited, and it can be selected from various methods which have been used for producing a thin layer from a solution. Specific examples thereof include a spraying method, a dipping method, a spin coating method and a roll coating method.
  • the firing method is not specially limited, and it includes a method of firing under atmospheric pressure, a method of firing under vacuum and a method of firing under pressure.
  • the firing temperature is limited to 300 to 650° C.
  • the reason for limiting the lower limit of the firing temperature to 300° C. is that when it is lower than 300° C., the decomposition of the material is insufficient or carbon formed by the decomposition of the solvent or stabilizer remains in the fired layer to decrease the electrical conductivity.
  • the reason for limiting the upper limit of the firing temperature to 650° C. is that when it exceeds 650° C., a layer obtained is crystalline and the electrical conductivity of the layer is low.
  • the firing temperature is preferably 300 to 600° C.
  • the time for the firing is preferably 0.01 to 10 hours.
  • the time for the firing is less than 0.01 hour, the decomposition of the material is insufficient or carbon formed by the decomposition of the solvent or stabilizer remains in the fired layer to decrease the electrical conductivity.
  • it exceeds 10 hours it is poor in economic performance.
  • the time for the firing is particularly preferably 0.1 to 10 hours.
  • the firing may be carried out a plurality of times as required.
  • the coating is reduction-treated after fired as described above.
  • the reduction method can be selected from reduction with a reducing gas, reduction with an inert gas and reduction by firing under vacuum.
  • the reducing gas is selected from hydrogen gas and steam of water.
  • the inert gas is selected from nitrogen gas and argon gas.
  • a mixed gas of an inert gas and oxygen gas may be used.
  • the temperature for the reduction is preferably 100 to 650° C. When the reduction temperature is lower than 100° C., it is difficult to sufficiently carry out the reduction. When it exceeds 650° C., the film is crystalline to decrease the electrical conductivity.
  • the reduction temperature is particularly preferably 200 to 500° C.
  • the time for the reduction is preferably 0.01 to 10 hours. When the reduction time is less than 0.01 hour, it is difficult to sufficiently carry out the reduction. When it exceeds 10 hours, it is poor in economic performance.
  • the reduction time is particularly preferably 0.1 to 10 hours.
  • the intended transparent electrically conductive layer I of the present invention is obtained by carrying out steps up to the reduction treatment as described above.
  • the sputtering target used for forming the transparent electrically conductive layer II on a predetermined substrate by a sputtering method may be any target which can give the transparent electrically conductive layer I.
  • Various sputtering targets may be used depending upon the composition (atomic ratio of In (In/(In+Zn)) of the intended transparent electrically conductive layer I and sputtering conditions.
  • sputtering target used for forming the transparent electrically conductive layer I on a predetermined substrate by an RF or DC magnetron sputtering to be sometimes referred to as "direct sputtering) method
  • direct sputtering sputtering targets (i) and (ii).
  • Target which is a sintered body formed from an oxide containing indium and zinc as main components and which has a predetermined value as an atomic ratio of In, In/(In+Zn).
  • target which has a predetermined value as an atomic ratio of In, In/(In+Zn) refers to a target which gives a final layer in which the atomic ratio of In, In/(In+Zn), is a predetermined value in the range of 0.50 to 0.90.
  • a target in which the atomic ratio of In, In/(In+Zn) is an intended value in the range of 0.45 to 0.9.
  • ZnO In 2 O 3
  • oxide-containing tablet Those similar to the above oxide-containing disk can be used as the oxide-containing tablet.
  • compositions and amounts of the oxide-containing disk and the oxide-containing tablet are properly determined such that the atomic ratio of In, In/(In+Zn), in a layer which is to be finally obtained is an intended value in the range of 0.50 to 0.90.
  • Each of the above sputtering targets (i) and (ii) preferably has a purity of at least 98%. When the purity is less than 98%, the resultant film sometimes shows decreased resistance to moist heat, decreased electrical conductivity or decreased light transmittance due to the presence of impurities.
  • the purity is more preferably at least 99%, further preferably at least 99.9%.
  • the relative density of the target is preferably at least 70%. When the relative density is less than 70%, the layer-forming rate is liable to decrease or the layer is liable to have degraded properties.
  • the relative density is more preferably at least 85%, further preferably at least 90%.
  • the above sputtering target (i) and the above oxide-containing disk and oxide-containing tablet (ii) can be produced as follows, for example.
  • an indium compound and a zinc compound are mixed, the resultant mixture is calcined to obtain a calcination product, and the calcination product is shaped and sintered to obtain an intended sintered body of an oxide.
  • the above indium compound and the zinc compound used as raw materials may be oxides or those which become oxides after fired (oxide precursors).
  • the indium oxide precursor and the zinc oxide precursor include sulfides, sulfates, nitrates, halides (chlorides, bromides, etc.), carbonates, organic acid salts (acetates, oxalates, propionates, naphthenates, etc.), alkoxides (methoxides, ethoxides, etc.) and organic metal complexes (acetylacetonates, etc.) of indium and zinc.
  • nitrates, organic acid salts, alkoxides or organic metal complexes for accomplishing complete thermal decomposition at a low temperature so that no impurities remain.
  • the above mixture of the indium compound and the zinc compound is preferably obtained by the following (A) solution method (coprecipitation method) or (B) physical mixing method.
  • a solution of the indium compound and the zinc compound is prepared, or a solution of at least the indium compound and a solution of at least the zinc compound are prepared, and in addition to the solution(s), a solution of a precipitant is prepared.
  • the above solutions are simultaneously or consecutively placed and mixed in a separately prepared container (which may contain a solvent as required) with stirring, to form a coprecipitate of the indium compound and the zinc compound.
  • a solution of a precipitant may be added to a solution of the indium compound and the zinc compound, or the procedure may be effected reversely.
  • the solution method will be detailed below with reference to a case where a solution of the indium compound and the zinc compound and a solution of a precipitant are separately prepared and these two solutions are placed and mixed in another container containing a solvent with stirring, to form a precipitate.
  • a solution of the indium compound and the zinc compound in a proper solvent (to be referred to as "'solution A" hereinafter) is prepared.
  • the solvent can be properly selected according to the solubility of the indium compound or the zinc compound.
  • it is selected from water, alcohols and aprotic polar solvents (DMSO, NMP, sulforane and THF).
  • DMSO aprotic polar solvents
  • preferred are alcohols having 1 to 5 carbon atoms (methanol, ethanol, isopropanol, methoxyethanol and ethylene glycol).
  • the concentration of each metal in Solution A is preferably 0.01 to 10 mol/liter. The reason therefor is that when it is less than 0.01 mol/liter, the productivity is poor, and that when it exceeds 10 mol/liter, a heterogeneous precipitate is formed.
  • added acids nitric acid and hydrochloric acid
  • polyhydric alcohols ethylene glycol
  • ethanolamines monoethanolamine and diethanolamine
  • Solution B A solution of a precipitant (to be referred to as "Solution B" hereinafter) is prepared together with the above Solution A.
  • the precipitant to be dissolved in Solution B is selected from alkalis (sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium hydroxide, ammonium carbonate and ammonium bicarbonate), and organic acids (formic acid, oxalic acid and citric acid).
  • the precipitate is formed as a hydroxide, an inorganic acid salt or an organic acid salt depending upon the precipitant.
  • the solvent for dissolving the precipitant and the solvent to be placed in a container in which a precipitate is formed are selected from the above solvents used for dissolving the indium compound and the zinc compound.
  • the solvents used for the above various solutions are preferably the same in kind, while different solvents may be used.
  • a precipitate is formed by any one of the above means, while the temperature at which the precipitate is formed can be a temperature equal to, or higher than, the melting point of the solvent and equal to, or lower than, the boiling point of the solvent.
  • the formed precipitate may be aged for 1 to 50 hours after formed.
  • the so-obtained precipitate is then solid-liquid separated and dried.
  • the solid-liquid separation of the precipitate is carried out by a conventional method such as centrifugal separation or filtration. After the solid-liquid separation, it is preferred to fully wash the precipitate with the same solvent as that used for Solution A or Solution B or other solvent for removing anion and alkali metal ion from the precipitate.
  • the drying after the solid-liquid separation is preferably carried out at 40 to 200° C. for 1 to 100 hours. When the drying temperature is lower than 40° C., the drying takes too long a time. When it is higher than 200° C., particles of the precipitate are liable to aggregate.
  • This method can be carried out in all the cases when the above indium compound is indium oxide or its precursor (regardless of being water-soluble or sparingly soluble) and when the above zinc compound is zinc oxide or its precursor regardless of being water-soluble or sparingly soluble).
  • the indium compound and the zinc compound are placed in a mixer such as a ball mill, a jet mill or a pearl mill and. these two compounds are homogeneously mixed.
  • the time for the mixing is preferably 1 to 200 hours. When the mixing time is less than 1 hour, the homogeneous mixing is liable to be insufficient. When it exceeds 200 hours, the productivity is poor.
  • the mixing time is particularly preferably 10 to 120 hours.
  • a mixture of the above indium compound and zinc compound is obtained by the above solution method or physical mixing method, and then this mixture is calcined.
  • this calcination step is preferably carried out at 200 to 1,200° C. for 1 to 100 hours.
  • the temperature is lower than 200° C. or when the time is less than 1 hour, the thermal decomposition of the indium compound and the zinc compound is insufficient.
  • the temperature is higher than 1,200° C. or when the time exceeds 100 hours, particles are sintered to form coarse particles.
  • the calcining temperature is 800 to 1,200° C. and the calcining time is 2 to 50 hours.
  • the calcination product is preferably milled, and it may be reduction-treated before or after it is milled.
  • the calcination product is preferably milled with a ball mill, a roll mill, a pearl mill or a jet mill so that it has a particle diameter of 0.01 to 1.0 ⁇ m.
  • the particle diameter is less than 0.01 ⁇ m, the powder is liable to aggregate and is difficult to handle. Moreover, it is difficult to obtain a dense sintered body. When it exceeds 1.0 ⁇ m, it is difficult to obtain a dense sintered body.
  • a mixture which is repeatedly calcined and milled can give a sintered body having a uniform composition.
  • the reduction method for the reduction treatment includes reduction using a reducing gas, firing in vacuum and reduction using an inert gas.
  • the reducing gas is selected from hydrogen, methane, Co and mixture of these gases with oxygen.
  • the inert gas is selected from nitrogen, argon and mixtures of these gases with oxygen.
  • the reduction temperature is preferably 100 to 800° C. When it is lower than 100° C., it is difficult to sufficiently carry out the reduction. When it exceeds 800° C., zinc oxide evaporates to change the composition.
  • the reduction temperature is particularly preferably 200 to 800° C.
  • the time for the reduction is preferably 0.01 to 10 hours. When it is less than 0.01 hour, it is difficult to sufficiently carry out the reduction. When it exceeds 10 hours, it is poor in economic performance.
  • the reduction time is particularly preferably 0.05 to 5 hours.
  • the above-obtained calcination product (including a powder of the calcination product) is then shaped and sintered.
  • This powder or calcination product comes under the electrically conductive material I of the present invention.
  • the above-obtained calcination powder is shaped by molding, casting or injection molding.
  • the calcination powder is preferably shaped by CIP (cold isostatic pressing) and subjected to sintering treatment to be described later.
  • the powder may be shaped in various forms suitable as a target.
  • shaping aids such as PVA (polyvinyl alcohol), MC (methyl cellulose), polywax and oleic acid may be used.
  • the shaped body is sintered by firing under atmospheric pressure or HIP (hot isotactic pressing).
  • the sintering temperature can be equal to, or higher than, a temperature at which the indium compound and the zinc compound are thermally decomposed to form an oxide, and it is generally preferably 800 to 1,700° C. When the temperature exceeds 1,700° C., zinc oxide and indium oxide sublime to alter the composition.
  • the sintering temperature is particularly preferably 1,200 to 1,700° C.
  • the time for sintering is preferably 1 to 50 hours, particularly preferably 2 to 10 hours.
  • the sintering may be carried out in a reducing atmosphere, and the reducing atmosphere includes atmospheres of reducing gases such as H 2 , methane and CO and inert gases such as Ar and N 2 .
  • reducing gases such as H 2 , methane and CO
  • inert gases such as Ar and N 2 .
  • zinc oxide and indium oxide easily evaporate, and it is therefore preferred to carry out the sintering under heat by HIP sintering, etc.
  • the sintering is carried out as above, whereby the intended target can be obtained.
  • the material for the substrate is not specially limited, and the substrate can be selected from substrates of various materials as required.
  • the substrate can be selected from various substrates in kind as compared with a case where the transparent electrically conductive layer I is formed by the above coating and thermal decomposition method.
  • the transparent substrate is selected from substrates formed of electrically insulating transparent polymers such as polycarbonate, polyarylate, polyester, polystyrene, a polyethersulfone-containing resin, an amorphous polyolefin and an acrylic resin, and substrates formed of electrically insulating transparent glass such as soda-lime glass, lead glass, borosilicate glass, high silica glass and alkali-free glass.
  • electrically insulating transparent polymers such as polycarbonate, polyarylate, polyester, polystyrene, a polyethersulfone-containing resin, an amorphous polyolefin and an acrylic resin
  • substrates formed of electrically insulating transparent glass such as soda-lime glass, lead glass, borosilicate glass, high silica glass and alkali-free glass.
  • the substrate may have an undercoating layer.
  • the undercoating layer include thin films of ZnO, SiO 2 and TiO 2 .
  • this substrate may have a crosslinked resin layer.
  • the crosslinked resin layer includes layers of an epoxy resin, a phenoxyether resin and an acrylic resin.
  • an adhesive layer and a gas barrier layer may be formed between the transparent polymer substrate and the crosslinked resin layer.
  • the material for the adhesive layer includes epoxy-, acrylurethane-, and phenoxyether-containing adhesives.
  • the material for the gas barrier layer includes an ethylene-vinyl alcohol copolymer, polyvinyl alcohol, polyacrylonitrile, polyvinylidene chloride and polyvinylidene fluoride.
  • the conditions for carrying out the sputtering differ depending upon a sputtering method and the characteristics of an apparatus used, and are therefore difficult to uniformly determine.
  • the conditions are preferably set as follows.
  • the vacuum degree in sputtering is approximately 1 ⁇ 10 -4 to 5 ⁇ 10 -2 Torr (approximately 1.3 ⁇ 10 -2 to 6.7 ⁇ 10 0 Pa), more preferably approximately 2 ⁇ 10 -4 to 1 ⁇ 10 -2 Torr (approximately 2.7 ⁇ 10 -2 to 1.3 ⁇ 10 -0 Pa), further preferably approximately 3 ⁇ 10 -4 to 5 ⁇ 10 -3 Torr (approximately 4.0 ⁇ 10 -2 to 6.7 ⁇ 10 -1 Pa).
  • the voltage for charging the target is preferably 200 to 500 V.
  • the vacuum degree in sputtering is less than 1 ⁇ 10 -4 Torr (the pressure is lower than 1 ⁇ 10 -4 Torr), the stability of plasma is poor.
  • it is higher than 5 ⁇ 10 -2 Torr (the pressure is higher than 5 ⁇ 10 -2 Torr) the voltage charged to the sputtering target cannot be increased.
  • the voltage charged to the target is less than 200 V, it is difficult to obtain a good-quality thin film, or the film-forming rate is limited, in some cases.
  • the ambient gas preferred is a mixture of an inert gas such as argon gas with oxygen gas.
  • an inert gas such as argon gas
  • oxygen gas oxygen gas is preferably 0.5:0.5-0.99:0.01.
  • the substrate temperature (temperature of substrate) can be properly set at a temperature in the range of room temperature to a temperature at which the substrate is free from deformation or alteration under heat, depending upon the heat resistance of the substrate. As the temperature for the heating increases, the production cost increases.
  • the substrate temperature is preferably between room temperature and 200° C.
  • a glass substrate is used, it is preferably between room temperature and 400° C.
  • the transparent electrically conductive layer I can be formed on a predetermined substrate not only by the above sputtering method, but also by a reactive sputtering method.
  • the sputtering target used in this case is specifically a target which is formed from an alloy of indium and zinc and has an atomic ratio of In, In/(In+Zn), of a predetermined value.
  • target which has an atomic ratio of In, In/(In+Zn), of a predetermined value refers to a target which gives a final layer having an atomic ratio of In, In/(In+Zn), of an intended value in the range of 0.50 to 0.90.
  • the above alloy target can be obtained, for example, by dispersing a predetermined amount of zinc powder or chips in molten indium and cooling the dispersion.
  • the alloy target preferably has a purity of at least 98% for the same reasons as those described with regard to the sputtering targets (i) and (ii). The purity is more preferably at least 99%, further preferably at least 99.9%.
  • the reactive sputtering sometimes greatly depends upon an apparatus used, and it is therefore difficult to uniformly determine the conditions for carrying out the reactive sputtering with the above alloy target.
  • the layer-forming conditions are therefore properly set depending upon the characteristics of an apparatus used, while the layer-forming conditions are preferably the same conditions as those in the above DC magnetron sputtering.
  • the transparent electrically conductive layer II of the present invention will be explained hereinafter.
  • the transparent electrically conductive layer II is a layer formed from an amorphous oxide containing, as main cation elements, at least one of third elements having a valence of at least 3 (e.g., tin (Sn), aluminum (Al), antimony (Sb), gallium (Ga) and germanium (Ge)) in addition to In and Zn, and in this layer, the atomic ratio of I, In/(In+Zn) is 0.50 to 090, and the atomic ratio of the total amount of the above third elements, (total third elements)/(In+Zn+total third elements), is 0.2 or less.
  • third elements having a valence of at least 3 e.g., tin (Sn), aluminum (Al), antimony (Sb), gallium (Ga) and germanium (Ge)
  • the atomic ratio of I, In/(In+Zn) is 0.50 to 090
  • the atomic ratio, In/(In+Zn), in the transparent electrically conductive layer II to 0.50 to 0.90 is the same as the reason explained in the description of the transparent electrically conductive layer I.
  • the atomic ratio, In/(In+Zn) is preferably 0.60 to 0.90.
  • the atomic ratio of In, In/(In+Zn), is more preferably 0.6 to 0.80 for a layer formed by the coating and thermal decomposition method, and 0.80 to 0.90 for a layer formed by the sputtering method.
  • the above atomic ratio is particularly preferably 0.60 to 0.75.
  • the reason for limiting the atomic ratio of the total amount of third elements, (total third elements)/(In+Zn+total third elements), to 0.2 or less is that when the atomic ratio of the total amount of third elements exceeds 0.2, ion scattering takes place to decrease the electrical conductivity of the layer to excess.
  • the atomic ratio of the total amount of third elements is preferably 0.10 or less, particularly preferably 0.02 to 0.10.
  • the transparent electrically conductive layer II Like the transparent electrically conductive layer I, crystalline layers have poor electrical conductivity as compared with amorphous layers even if these layers have the same composition.
  • the transparent electrically conductive layer II is also therefore limited to amorphous layers. Further, when the atomic ratio, In/(In+Zn), of layers obtained by the coating and thermal decomposition method exceeds 0.80, the layers may show poor electrical conductivity in some cases.
  • the above amorphous oxide can be used as a transparent electrically conductive layer when formed as a thin layer.
  • the thickness of this layer can be properly selected depending upon use and a material of a substrate on which the transparent electrically conductive layer II is formed, while it is generally in the range of 3 nm to 3,000 nm like the transparent electrically conductive layer I.
  • the layer thickness is less than 3 nm, the electrical conductivity is liable to be insufficient.
  • it exceeds 3,000 nm the light transmittance is liable to decrease.
  • the transparent electrically conductive layer II of the above amorphous oxide is a transparent electrically conductive layer having practically sufficient electrical conductivity and light transmittance and having excellent resistance to moist heat and etching properties.
  • the above transparent electrically conductive layer II can be also produced by any one of various methods such as an coating and thermal decomposition method, a sputtering method and a CVD method.
  • an coating and thermal decomposition method or a sputtering method is preferred.
  • Sn is particularly preferred. When Sn is used, the electrical conductivity is further improved.
  • the production of the transparent electrically conductive layer II by the coating and thermal decomposition method differs from the production of the transparent electrically conductive layer I by the coating and thermal decomposition method in that there is prepared a coating solution containing a predetermined amount of a compound of at least one of third elements having a valence of at least 3 (e.g., tin (Sn), aluminum (Al), antimony (Sb), gallium (Ga) and germanium (Ge)) in addition to the indium compound and the zinc compound.
  • a coating solution containing a predetermined amount of a compound of at least one of third elements having a valence of at least 3 (e.g., tin (Sn), aluminum (Al), antimony (Sb), gallium (Ga) and germanium (Ge) in addition to the indium compound and the zinc compound.
  • the transparent electrically conductive layer I is the same as the production of the transparent electrically conductive layer I in other points, i.e., the kinds of the indium compound and the zinc compound, the method of preparing the coating solution, the kind of the substrate, the firing method and the reducing: method.
  • the concentration of the total content of In, Zn and the third element(s) (Sn, Al, Sb, Ga, Ge) in the coating solution is preferably 0.01 to 10 mol %, particularly preferably 0.1 to 5 mol %.
  • the "predetermined amount of a compound of third element” refers to an amount which can give a film in which the atomic ratio of the total amount of third elements (Sn, Al, Sb, Ga, Ge, etc.), (total third elements)/(In+Zn+total third elements), is an intended value equal to, or smaller than, 0.2.
  • Sn compound used as a compound of the third element in the production of the transparent electrically conductive layer II by the coating and thermal decomposition method include tin acetate (valence of 2), dimethoxytin, diethoxytin, dipropoxytin, dibutoxytin, tetramethoxytin, tetraethoxytin, tetrapropoxytin, tetrabutoxytin, tin chloride (valence of 2) and tin chloride (valence of 4).
  • the tin compounds whose tin has a valence of 2 are converted to tin compounds whose tin has a valence of 4 in a firing step.
  • Al compound examples include aluminum chloride, trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum and tributoxyaluminum.
  • Sb compound examples include antimony trichloride (valence of 3), antimony chloride (valence of 5), trimethoxyantimony, triethoxyantimony, tripropoxyantimony and tributoxyantimony.
  • Ga compound examples include gallium chloride (valence of 3), trimethoxygallium, triethoxygallium, tripropoxygallium and tributoxygallium.
  • Ge compound examples include germanium chloride (valence of 4), tetramethoxyqermanium, tetraethoxygermanium, tetrapropoxygermanium and tetrabutoxygermanium.
  • the production of the transparent electrically conductive layer II by the sputtering method can be carried out in the same manner as in the production of the transparent electrically conductive layer I by the sputtering method (RF or DC magnetron sputtering method and reactive sputtering method) except for a point where the composition of the target used is different.
  • sputtering target used for forming the transparent electrically conductive layer II on a predetermined substrate by the direct sputtering (RF or DC magnetron sputtering) method are the following sputtering targets (iii) and (iv).
  • Target which is a target of a sintered body formed from an oxide containing at least one of third elements having a valence of at least 3 (e.g., Sn, Al, Sb, Ga and Ge) in addition to indium oxide and zinc oxide, and which has predetermined values as an atomic ratio of In, In/(In+zn), and as an atomic ratio of the total amount of third elements, (total third elements)/(In+Zn+total third elements).
  • third elements having a valence of at least 3 e.g., Sn, Al, Sb, Ga and Ge
  • target which has a predetermined value as an atomic ratio of In, In/(In+Zn) refers to a target which gives a final layer in which the atomic ratio of In, In/(In+Zn), is a predetermined value in the range of 0.50 to 0.90. Specifically, there is used a target in which the atomic ratio of In, In/(In+Zn), is an intended value in the range of 0.45 to 0.9.
  • target which has a predermined value as an atomic ratio of the total amount of third elements, (total third elements)/(In+zn+total third elements) refers to a target which gives a final layer in which the atomic ratio of the total amount of third elements, (total third elements)/(In+Zn+total third elements), is a predetermined value equal to, or less than, 0.2.
  • oxide-containing tablet Those similar to the above oxide-containing disk can be used as the oxide-containing tablet. Or, there may be used a tablet formed substantially from a spinel structure compound of Zn 2 SnO 4 , Zn 7 Sb 2 O 12 or ZnAl 2 O 4 or a tablet formed substantially from a tri-rutile structure compound of ZnSb 2 O 6 .
  • the third element is contained in at least one of the oxide-containing disk and the oxide-containing tablet, and the compositions and amounts of the oxide-containing disk and the oxide-containing tablet are properly determined such that the atomic ratio of In, In/(In+Zn), in a layer which is to be finally obtained is an intended value in the range of 0.50 to 0.90 and that the atomic ratio of the total amount of third elements, (total third elements)/(In+Zn+total third elements) is an intended value equal to, or less than, 0.2.
  • Each of the above sputtering targets (iii) and (iv) preferably has a purity of at least 98%. When the purity is less than 98%, the resultant film sometimes shows decreased resistance to moist heat, decreased electrical conductivity or decreased light transmittance due to the presence of impurities. The purity is more preferably at least 99%, further preferably at least 99.9%.
  • the relative density of the target is preferably at least 70%. When the relative density is less than 70%, the layer-forming rate is liable to decrease or the layer is liable to have degraded properties. The relative density is more preferably at least 85%, further preferably at least 90%.
  • the above sputtering target (iii) and the above oxide-containing disk and oxide-containing tablet (iv) can be obtained, for example, in the same manner in the production of the above sputtering target (i) and the above oxide-containing disk and oxide-containing tablet (ii) in the same manner as in the solution method (coprecipitation method) except that a solution containing a predetermined amount of a compound of intended third element in addition to the indium compound and the zinc compound is allowed to react with an alkaline solution to form a precipitate, or in the same manner as in the above physical mixing method except that a predetermined amount of oxide of intended third element or a compound which forms an oxide of intended third element when fired is added to the starting materials to obtain a mixture.
  • the tin compound is selected from tin acetate, tin oxalate, tin alkoxides (dimethoxytin, diethoxytin, dipropoxytin, dibutoxytin, tetramethoxytin, tetraethoxytin, tetrapropoxytin and tetrabutoxytin), tin chloride, tin fluoride, tin nitrate and tin sulfate, and is used in a desired amount.
  • tin oxide or a compound which forms tin oxide when fired is used in a desired amount.
  • Those tin compounds whose tin has a valence of 2 are converted to tin compounds whose tin has a valence of 4 in a firing step.
  • the antimony compound is selected from antimony chloride, antimony fluoride, antimony alkoxides (trimethoxyantimony, triethoxyantimony, tripropoxyantimony and tributoxyantimony), antimony sulfate, and antimony hydroxide, and is used in a desired amount.
  • antimony oxide or a compound which forms antimony oxide when fired specifically, any one of the above compounds used in the solution method, is used in a desired amount.
  • the gallium compound is selected from gallium chloride, gallium alkoxides (trimethoxygallium, triethoxygallium, tripropoxygallium and tributoxygallium) and gallium sulfate, and is used in a desired amount.
  • gallium oxide or a compound which forms gallium oxide when fired specifically, any one of the above compounds used in the solution method, is used in a desired amount.
  • the germanium compound is selected from germanium chloride and germanium alkoxides (tetramethoxygermanium, tetraethoxygermanium, tetrapropoxygermanium and tetrabutoxygermanium), and is used in a desired amount.
  • germanium or a compound which forms germanium oxide when fired specifically, any one of the above compounds used in the solution method, is used in a desired amount.
  • both a powder formed from at least one of compounds prepared by incorporating at least one of the above third elements into hexagonal laminar compounds of In 2 O 3 (ZnO) m (m 2-20), and a powder formed substantially from at least one of the above compounds, and In 2 O 3 and/or ZnO come under the electrically conductive material II of the present invention.
  • the transparent electrically conductive layer II can be formed on a predetermined substrate not only by the above direct sputtering method, but also by a reactive sputtering method.
  • the production of the transparent electrically conductive layer II by the reactive sputtering method can be carried out in the same manner as in the production of the transparent electrically conductive layer I by the reactive sputtering method except for the use of a sputtering target which is formed of an alloy of indium, zinc and at least one of third elements having a valence of at least 3 (e.g., Sn, Al, Sb, Ga and Ge) and in which the atomic ratio of In, In/(In+Zn), and the atomic ratio of the total amount of third elements, (total third elements)/(In+Zn+total third elements), are respectively predetermined values.
  • a sputtering target which is formed of an alloy of indium, zinc and at least one of third elements having a valence of at least 3 (e.g., S
  • sputtering target in which the atomic ratio of In, In/(In+Zn), is a predetermined value refers to a target which gives a layer in which the atomic ratio of In, In/(In+Zn), is a desired value in the range of 0.50 to 0.90. Specifically, there is used a target in which the atomic ratio of In, In/(In+Zn), is in the range of 0.45 to 0.9.
  • target in which the atomic ratio of the total amount of third elements, (total third elements)/(In+Zn+total third element), is a predetermined value refers to a target which gives a layer in which the atomic ratio of the amount of third elements, (total third elements)/(In+Zn+total third elements), is a desired value equal to, or less than, 0.2.
  • the above alloy target is obtained by dispersing, in a molten indium, a predetermined amount of a powder or chips of zinc and a predetermined amount of a powder of chips of single element (solid) of at least one of third elements having a valence of at least 3 (e.g., a powder or chips of single element (solid) of at least one third element selected from the group consisting of Sn, Al, Sb, Ga and Ge), and then cooling the dispersion. Further, it can be also obtained by melting an alloy of indium and at least one of third elements having a valence of at least 3 (e.g., Sn, Al Sb, Ga and Ge), dispersing a powder or chips of zinc in the molten alloy, and cooling the dispersion.
  • the purity of the above alloy target is preferably at least 98%, more preferably at least 99%, further preferably at least 99.9%.
  • the transparent electrically conductive layer I and transparent electrically conductive layer II of the present invention which can be produced by the above-explained coating and thermal decomposition method or sputtering method, are transparent electrically conductive layers having practically sufficient electrical conductivity and light transmittance and having excellent resistance to moist heat and etching properties.
  • the transparent electrically conductive layer I and. transparent electrically conductive layer II of the present invention which have the above properties, are suitable as transparent electrodes in various fields such as a transparent electrode for a liquid crystal display device, a transparent electrode for an electroluminescence device and a transparent electrode for a solar cell, base materials for forming the above transparent electrodes by an etching method, films for the prevention of electrostatic charge or heaters for deicing on window glass.
  • the electrically conductive transparent film of the present invention is characterized in that the above transparent electrically conductive layer I or the above transparent electrically conductive layer II is formed on a transparent polymer substrate in the form of a film or a sheet directly or through at least a crosslined resin layer.
  • the above transparent polymer substrate in the form of a film or a sheet is selected from substrates formed of a polycarbonate resin, a polyarylate resin, a polyester resin, a polyethersulfone-containing resin, an amorphous polyolefin resin, a polystyrene resin and an acrylic resin.
  • the light transmittance thereof is preferably at least 70%. When it is less than 70%, the substrate is unsuitable as a transparent substrate.
  • a substrates having a light transmittance of at least 80% is more preferred, and a substrate having a light transmittance of at least 90% is further preferred.
  • the thickness of the transparent polymer substrate is preferably 15 ⁇ m to 3 mm, more preferably 50 ⁇ m to 1 mm.
  • the transparent electrically conductive layer formed on the transparent polymer substrate directly or through a crosslinked resin layer may be any one of the transparent electrically conductive layer I and the transparent electrically conductive layer II as described above, while the layer thickness thereof is preferably 3 to 3,000 nm. When it is less than 3 nm, no sufficient electrical conductivity is obtained. When it exceeds 3,000 nm, the light transmittance may decrease, or the transparent electrically conductive layer may undergo cracking when the electrically conductive transparent layer is handled.
  • the above layer thickness is more preferably 5 to 1,000 nm, further preferably 10 to 800 nm.
  • a layer formed of an epoxy resin, a phenoxyether resin or an acrylic resin is preferred as the crosslinked resin layer.
  • an adhesive layer and a gas barrier layer may be formed between the transparent polymer layer and the crosslinked resin layer.
  • the material for the adhesive layer is selected from epoxy-, acrylurethane- and phenoxyether-containing adhesives.
  • the material for the gas barrier layer is selected from an ethylene-vinyl alcohol copolymer, polyvinyl alcohol, polyacrylonitrile, polyvinylidene chloride and polyvinylidene fluoride.
  • the transparent electrically conductive layer is formed on one surface of the transparent polymer substrate, and the other surface of the transparent polymer substrate may be provided with a gas barrier layer, a hard coating layer and an anti-reflection layer.
  • the electrically conductive transparent film of the present invention has practically sufficient electrical conductivity and light transmittance, and the transparent electrically conductive layer constituting the electrically conductive transparent film has excellent resistance to moist heat, so that, even under a high-humidity environment.
  • the electrically conductive transparent film shows a small decrease in electrical conductivity with time or shows stable electrical conductivity. Further, the transparent electrically conductive layer constituting the electrically conductive transparent film is excellent in etching properties.
  • the electrically conductive transparent film of the present invention which has the above properties, is suitable as a base material for forming transparent electrodes, by an etching method, in various fields such as a transparent electrode for a liquid crystal display device, a transparent electrode for an electroluminescence device and a transparent electrode for a solar cell, or a film for the prevention of electrostatic charge or a heater for deicing on window glass.
  • the above electrically conductive transparent film can be produced by various methods.
  • the transparent electrically conductive layer I or the transparent electrically conductive layer II is formed on the transparent polymer substrate in the form of a film directly or through at least the crosslinked resin layer, the use of a sputtering method such as RF or DC magnetron sputtering or reactive sputtering is preferred, in view of the performance and productivity of the transparent electrically conductive layer, or since the production can be carried out while the substrate temperature is maintained at a low temperature.
  • the production of the transparent electrically conductive layer I or the transparent electrically conductive layer II by a sputtering method is as explained already,
  • the electrically conductive transparent glass which is another electrically conductive transparent substrate of the present invention will be explained hereinafter.
  • the electrically conductive transparent glass of the present invention is characterized in that the above transparent electrically conductive layer I or transparent electrically conductive layer II is formed on a transparent glass substrate.
  • the film shows poor electrical conductivity in some cases.
  • the above transparent glass substrate can be selected from substrates of various transparent glass films or plates such as substrates of soda-line glass, lead glass, borosilicate glass, high silica glass and alkali-free glass. The kind and thickness thereof are properly selected depending upon intended use of the electrically conductive transparent glass.
  • the transparent electrically conductive layer formed on the transparent glass substrate may be any one of the transparent electrically conductive layer I and the transparent electrically conductive layer II as described above, while the layer thickness thereof is preferably 3 to 3,000 nm. When it is less than 3 nm, no sufficient electrical conductivity is obtained. When it exceeds 3,000 nm, the electrically conductive transparent glass shows decreased light transmittance.
  • the above layer thickness is more preferably 5 to 1,000 nm, further preferably 10 to 800 nm.
  • the electrically conductive transparent glass of the present invention has practically sufficient electrical conductivity and light transmittance, and the transparent electrically conductive layer constituting the electrically conductive transparent glass has excellent resistance to moist heat, so that, even under a high-humidity environment, the electrically conductive transparent glass shows a small decrease in electrical conductivity with time or shows stable electrical conductivity. Further, the transparent electrically conductive layer constituting the electrically conductive transparent glass is excellent in etching properties.
  • the electrically conductive transparent glass of the present invention which has the above properties, is suitable as a base material for forming transparent electrodes, by an etching method, in various fields such as a transparent electrode for a liquid crystal display device, a transparent electrode for an electroluminescence device and a transparent electrode for a solar cell, or a film for the prevention of electrostatic charge or a heater for deicing on window glass.
  • the above electrically conductive transparent glass can be produced by various methods.
  • the production by the coating and thermal decomposition method is preferred for producing it at a low cost with easily controlling its composition, and the production by the sputtering method such as RF or DC magnetron sputtering or reactive sputtering is preferred for producing a layer having high performance with high productivity.
  • the production of the transparent electrically conductive layer I or the transparent electrically conductive layer II by the coating and thermal decomposition method or the sputtering method are as already described.
  • the above electrically conductive material. I may be formed substantially of at least one of hexagonal laminar compounds of the above general formula; or may be formed substantially of a material containing crystalline or amorphous In 2 O 3 and/or ZnO in addition to at least one of hexagonal laminar compound of the above general formula.
  • the electrically conductive material I can be obtained in the step of producing the above sputtering targets (i) and (ii), while the production process thereof is not limited thereto.
  • third elements having a valence of at least 3 e.g., tin (Sn), aluminum (Al), antimony (Sb), gallium (Ga
  • the electrically conductive material II can be obtained in the step of producing the above sputtering targets (i) and (ii), while the production process thereof is not limited thereto.
  • the above electrically conductive material II may be formed substantially from at least one of the above compounds or may be formed substantially from a material containing crystalline or amorphous In 2 O 3 and/or ZnO in addition to at least one of the above compounds.
  • Transparent electrically conductive layers I were produced in the following manner, by a coating and thermal decomposition method using indium acetate as an indium compound, anhydrous zinc acetate as a zinc compound, 2-methoxymethanol as a solvent, monoethanolamine as a stabilizer, and a quartz glass plate as a substrate.
  • a quartz glass plate 70 ⁇ 20 ⁇ 1.5 mm was dipped in the above-obtained coating solution to carry out a dip-coating (coating rate: 1.2 cm/minute), and then, the coating was calcined in an electric oven at 500° C. for 10 minutes.
  • the above procedure of calcination after the dip-coating was repeated up to 10 times as a total, and further, the coating was fired at 500° C. for 1 hour.
  • the coating was reduced under vacuum (1 ⁇ 10 -2 torr) at 400° C. for 2 hours to give an intended transparent electrically conductive layer I.
  • the so-obtained four transparent electrically conductive layers I were measured by XRD (X-ray diffraction) to show that they were all amorphous oxides of In and Zn.
  • FIG. 1 shows an XRD measurement result of the transparent electrically conductive layer I obtained by the firing at 500° C.
  • the transparent electrically conductive layers I were measured for a composition by X-ray photoelectron spectral analysis (XPS) to show that the atomic ratio of In, In/(In+Zn), in each layer was 0.67.
  • XPS X-ray photoelectron spectral analysis
  • the transparent electrically conductive layers I were measured for a thickness on the basis of their electron microscopic photographs to show 200 nm each.
  • the above transparent electrically conductive layers I were measured for a surface resistance by a four probe method and for a transmittance to visible light (wavelength 550 nm), and Table 1 shows the results. Further, the above transparent electrically conductive layers I were tested for a resistance to moist heat under conditions of 40° C. and 90% RH, and measured for a surface resistance after a test time of 1,000 hours. Table 1 also shows the results. Further, the transparent electrically conductive layers I were measured for an etching rate by the use of a liquid prepared by diluting an etching solution of which the hydrochloric acid:nitric acid:water amount ratio was 1:0.08:1 (molar ratio), 10 times. Table 1 also shows the results.
  • a transparent electrically conductive layer (thickness 200 nm) was obtained in the same manner as in Example 1 (calcining temperature 500° C.) except that the firing temperature was changed to 700° C.
  • the so-obtained transparent electrically conductive layer was measured by XRD to show that it was crystalline. It was also measured for a composition by XPS to show that the atomic ratio of In, In/(In+Zn), was 0.67.
  • the above electrically conductive layer was also measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 1. Table 1 shows the results.
  • Example 1 Thereafter, the procedures described in Example 1 were repeated to give four transparent electrically conductive layers I (thickness 200 nm), the firing temperatures for which were different, i.e., 300° C., 400° C., 500° C. and 600° C., as shown in Table 1.
  • the so-obtained four transparent electrically conductive layers I were measured by XRD to show they were all amorphous oxides of In and Zn. These transparent electrically conductive layers I were measured for a composition by XPS to show that the atomic ratio of In, In/(In+Zn), in each layer was 0.75.
  • the above electrically conductive layers I were also measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and they were also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layers I were measured for an etching rate in the same manner as in Example 1. Table 1 shows the results.
  • a transparent electrically conductive layer (thickness 200 nm) was obtained in the same manner as in Example 2 (calcining temperature 500° C.) except that the firing temperature was changed to 700° C.
  • the so-obtained transparent electrically conductive layer was measured by XRD to show that it was crystalline. It was also measured for a composition by XPS to show that the atomic ratio of In, In/(In+Zn), was 0.75.
  • the above electrically conductive layer was also measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 1. Table 1 shows the results.
  • Example 1 Thereafter, the procedures described in Example 1 were repeated to give four transparent electrically conductive layers I (thickness 200 nm), the firing temperatures for which were different, i.e., 300° C., 400° C., 500° C. and 600° C., as shown in Table 1.
  • the so-obtained four transparent electrically conductive layers I were measured by XRD to show they were all amorphous oxides of In and Zn. These transparent electrically conductive layers I were measured for a composition by XPS to show that the atomic ratio of In, In/(In+Zn), in each film was 0.55.
  • the above electrically conductive layers I were also measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and they were also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layers I were measured for an etching rate in the same manner as in Example 1. Table 1 shows the results.
  • a transparent electrically conductive layer (thickness 200 nm) was obtained in the same manner as in Example 3 (calcining temperature 500° C.) except that the firing temperature was changed to 700° C.
  • the so-obtained transparent electrically conductive layer was measured by XRD to show that it was crystalline. It was also measured for a composition by XPS to show that the atomic ratio of In, In/(In+Zn), was 0.55.
  • the above electrically conductive layer was also measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 1. Table 1 shows the results.
  • a transparent and homogeneous coating solution was obtained in the same manner as in Example 1 except that the atomic ratio of In, In/(In+Zn), in the coating solution was changed to 0.50.
  • a transparent electrically conductive layer (thickness 200 nm) was obtained in the same manner as in Example 1 (calcining temperature 500° C.) except that the firing temperature was changed to 700° C.
  • the so-obtained transparent electrically conductive layer was measured for a composition by XPS to show that the atomic ratio of In, In/(In+Zn), was 0.50.
  • the above electrically conductive layer was also measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 1. Table 1 shows the results.
  • a transparent and homogeneous coating solution was obtained in the same manner as in Example 1 except that the atomic ratio of In, In/(In+Zn), in the coating solution was changed to 0.33.
  • Example 2 Thereafter, the coating, the firing (calcining temperature 500° C., firing temperature 500° C.) and the reduction treatment were carried out in the same manner as in Example 1 to give a transparent electrically conductive layer (thickness 200 nm).
  • the so-obtained transparent electrically conductive layer was measured for a composition by XPS to show that: the atomic ratio of In, In/(In+Zn), was 0.33.
  • the above electrically conductive layer was also measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 1. Table 1 shows the results.
  • a transparent and homogeneous coating solution was obtained in the same manner as in Example 1 except that the atomic ratio of In, In/(In+Zn), in the coating solution was changed to 0.80.
  • the so-obtained transparent electrically conductive layer was measured for a composition by XPS to show that the atomic ratio of In, In/(In+Zn), was 0.80.
  • the above electrically conductive layer was measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 1. Table 1 shows the results.
  • the so-obtained thin layer of indium oxide was measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the thin layer of indium oxide was measured for an etching rate in the same manner as in Example 1. Table 1 shows the results.
  • ITO thin layer (Sn 4 at %, thickness 200 nm) was obtained in the same manner as in Comparative Example 7 except that 0.16 g of Sn(OC 4 H 9 ) 2 was added to the same coating solution as that used in Comparative Example 8.
  • the so-obtained ITO thin layer was measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the ITO thin layer was measured for an etching rate in the same manner as in Example 1. Table 1 shows the results.
  • the transparent electrically conductive layers I in Examples 1 to 3 formed of amorphous oxides in which the atomic ratio of In, In/(In+Zn), was 0.55 to 0.75, had electrical conductivity similar to or higher than the ITO layer in Comparative Example 8. Further, each of the transparent electrically conductive layers I in Examples 1 to 3 had excellent transmittance to visible light. Further, the surface resistance of each of the transparent electrically conductive layers I in Examples 1 to 3 showed almost no change between after and before the test on resistance to moist heat. This shows that the transparent electrically conductive layers I in Examples 1 to 3 were excellent in resistance to moist heat. Further, the transparent electrically conductive layers I in Examples 1 to 3 showed high etching rates than the ITO layer in Comparative Example 8, which shows that the transparent electrically conductive layers I in Examples 1 to 3 were excellent in etching properties.
  • the electrically conductive layers in Comparative Examples 1 to 3 in which the atomic ratio of In, In/(In+Zn), was 0.55 to 0.75, but which were formed of crystalline oxides, had very low electrical conductivity.
  • the transparent electrically conductive layer in Comparative Example 5 in which the atomic ratio, In/(In+Zn), was outside the range defined by the present invention, had poor electrical conductivity as compared with the transparent electrically conductive layers I in Examples where the kinds of starting materials, the firing conditions and reduction conditions were the same.
  • a transparent electrically conductive layer II was produced in the following manner, by a coating and thermal decomposition method using indium acetate as an indium compound, anhydrous zinc acetate as a zinc compound, dibutoxytin as a third element, 2-methoxymethanol as a solvent, monoethanolamine as a stabilizer, and a quartz glass plate as a substrate.
  • Example 1 30 grams of a transparent and homogeneous solution (corresponding to the coating solution in Example 1) was prepared from 2-methoxymethanol, monoethanolamine, indium acetate and anhydrous zinc acetate in the same manner as in Example 1.
  • Example 2 a glass plate (7059: 70 ⁇ 20 ⁇ 1.5 mm, supplied by Corning) was dipped in the above-obtained coating solution under the same conditions as those in Example 1, and the coating was calcined in an electric oven at 500° C. for 10 minutes. The above procedure of calcination after the dip-coating was repeated up to 10 times as a total, and further, the coating was fired at 500° C. for 1 hour.
  • the coating was reduced under vacuum (1 ⁇ 10 -2 torr) at 400° C. for 2 hours to give an intended transparent electrically conductive layer II (thickness 200 nm).
  • the above-obtained transparent electrically conductive layer II was measured by XRD to show it was formed of an amorphous oxide of In, Zn and Sn. Further, the above electrically conductive layer II was also measured for a surface resistance and a transmittance to visible light i:n the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layer II was measured for an etching rate in the same manner as in Example 1. Table 2 shows the results.
  • a transparent electrically conductive layer II (thickness 200 nm) was prepared from the above coating solution in the same manner as in Example 4.
  • the above-obtained transparent electrically conductive layer II was measured by XRD to show it was formed of an amorphous oxide of In, Zn and Al. Further, the above electrically conductive layer II was also measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layer II was measured for an etching rate in the same manner as in Example 1. Table 2 shows the results.
  • a transparent electrically conductive layer II (thickness 200 nm) was prepared from the above coating solution in the same manner as in Example 4.
  • the above-obtained transparent electrically conductive layer II was measured by XRD to show it was formed of an amorphous oxide of In, Zn and Sb. Further, the above electrically conductive layer II was also measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layer II was measured for an etching rate in the same manner as in Example 1. Table 2 shows the results.
  • a transparent electrically conductive layer II (thickness 200 nm) was prepared from the above coating solution in the same manner as in Example 4.
  • the above-obtained transparent electrically conductive layer II was measured by XRD to show it was formed of an amorphous oxide of In, Zn and Ga. Further, the above electrically conductive layer II was also measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layer II was measured for an etching rate in the same manner as in Example 1. Table 2 shows the results.
  • a transparent electrically conductive layer II (thickness 200 nm) was prepared from the above coating solution in the same manner as in Example 4.
  • the above-obtained transparent electrically conductive layer II was measured by XRD to show it was formed of an amorphous oxide of In, Zn and Ge. Further, the above electrically conductive layer II was also measured for a surface resistance and a transmittance to visible light in the same manner as in Example 1, and it was also tested for resistance to moist heat in the same manner as in Example 1 and measured for a surface resistance after a test time of 1,000 hours. Further, the transparent electrically conductive layer II was measured for an etching rate in the same manner as in Example 1. Table 2 shows the results.
  • the transparent electrically conductive layers II in Examples 4 to 8 formed of an amorphous oxide of In, Zn and a third element (Sn, Al, Sb, Ga or Ge), had higher electrical conductivity than the transparent electrically conductive layers I in Examples 1 to 3, which contained no third element. Further, the transparent electrically conductive layers II in Examples 4 to 8 had excellent transmittance to visible light. Moreover, the surface resistance of each of the transparent electrically conductive layers II in Examples 4 to 8 showed almost no change between after and before the test on resistance to moist heat. This shows that the transparent electrically conductive layers II in Examples 4 to 8 were excellent in resistance to moist heat.
  • the etching rates of the transparent electrically conductive layers II in Examples 4 to 8 are higher than the etching rate of the ITO layer in Comparative Example 8 shown in Table 1, which shows that the transparent electrically conductive layers II in Examples 4 to 8 were excellent in etching properties.
  • a biaxially oriented polyester film having a thickness of 125 ⁇ m was used as a transparent polymer substrate and a sintered body formed of a mixture of indium oxide and zinc oxide in which the atomic ratio of In, In/(In+Zn), was 0.67 was used as a sputtering target for producing an electrically conductive transparent film in the following manner.
  • the voltage to be applied to the target was set at 420 V
  • the substrate temperature was set at 60° C.
  • a transparent electrically conductive layer I having a thickness of 250 nm was formed on the transparent polymer substrate by DC magnetron direct sputtering.
  • the transparent electrically conductive layer I was measured for a thickness by a probe method using DEKTAK 3030 supplied by Sloan (The same measurement was carried out in Examples and Comparative Examples to be described below).
  • the so-obtained electrically conductive transparent film was analyzed for an atomic ratio of In, In/(In+Zn), in the transparent electrically conductive layer I by ICP analysis (Inductively Coupled Plasma Emission Spectrochemical Analysis; using SPS-15OOVR supplied by Seiko Instruments Inc., the same measurement was carried out in Examples and Comparative Examples to be described below). As a result, it was shown that the atomic ratio of In, In/(In+Zn), was the same as that of the sputtering target, or 0.67.
  • the above transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction measurement (using Rotor Flex Ru-2000B, supplied by Rigaku k.k., the same measurement was carried out in Examples and Comparative Examples to be described below) to show that it was amorphous.
  • the result of the X-ray diffraction measurement was substantially the same as that shown in FIG. 1.
  • the above electrically conductive transparent film was immersed in a liquid prepared by diluting an etching solution of which the hydrochloric acid:nitric acid:water amount ratio was 1:0.08:1 (molar ratio), with water 10 times, and a period of time was measured until the resistance value thereof become at least 2 M ⁇ .
  • the etching rate of the transparent electrically conductive layer I was calculated on the basis of the period of time. Table 3 shows the results.
  • a biaxially oriented polyester film having a thickness of 125 ⁇ m was used as a transparent polymer substrate and a sputtering target formed of a mixture of indium and zinc in which the atomic ratio of In, In/(In+Zn), was 0.67 was used as such for producing an electrically conductive transparent film in the following manner.
  • the voltage to be applied to the target was set at 420 V
  • the substrate temperature was set at 140° C.
  • a transparent electrically conductive layer I having a thickness of 280 nm was formed on the transparent polymer substrate by reactive sputtering.
  • the transparent electrically conductive layer I was formed of a composition of indium oxide and zinc oxide, and. the atomic ratio of In, In/(In+Zn), in the transparent electrically conductive layer I was analyzed by ICP to show 0.67. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a biaxially oriented polyester film having a thickness of 125 ⁇ m was used as a transparent polymer substrate and a sputtering target formed of a mixture containing indium, zinc and Sn in which the atomic ratio of In, In/(In+Zn), was 0.67 and the atomic ratio of Sn as a third element, Sn/(In+Zn+Sn), was 0.04 was used as such for producing an electrically conductive transparent film in the following manner.
  • the voltage to be applied to the target was set at 350 V
  • the substrate temperature was set at 80° C.
  • a transparent electrically conductive layer II having a thickness of 300 nm was formed on the transparent polymer substrate by sputtering.
  • the transparent electrically conductive layer II was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.67 and the atomic ratio of Sn as a third element, Sn/(In+Zn+Sn), was 0.04. Further, the transparent electrically conductive layer II was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer II was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • the sputtering output was, set at 100 W, the substrate temperature was set at 20° C., and a transparent electrically conductive layer I having a thickness of 200 nm was formed on the transparent polymer substrate by RF magnetron direct sputtering.
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.70. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive layer I having a thickness of 200 nm was formed on a transparent polymer substrate in the same manner as in Example 12 except that the sputtering target was replaced with a target of a sintered body formed of a hexagonal laminar compound of In 2 O 3 (ZnO) 4 , and indium oxide (In 2 O 3 ) in which the atomic ratio of In, In/(In+Zn), was 0.70.
  • ZnO hexagonal laminar compound of In 2 O 3
  • In 2 O 3 indium oxide
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.74. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive layer I having a thickness of 200 nm was formed on a transparent polymer substrate in the same manner as in Example 13 except that the RF magnetron direct sputtering apparatus was replaced with a DC magnetron direct sputtering apparatus.
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.73. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive layer I having a thickness of 180 nm was formed on a transparent polymer substrate in the same manner as in Example 12 except that the sputtering target was replaced with a target of a sintered body formed of a hexagonal laminar compound of In 2 O 3 (ZnO) 4 , and indium oxide (In 2 O 3 ) in which the atomic ratio of In, In/(In+Zn), was 0.75.
  • ZnO hexagonal laminar compound of In 2 O 3
  • In 2 O 3 indium oxide
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.79. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive layer I having a thickness of 200 nm was formed on a transparent polymer substrate in the same manner as in Example 15 except that the substrate temperature in forming the film was set at 80° C.
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.78. Further, the transparent electrically conductive film I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive layer I having a thickness of 220 nm was formed on a transparent polymer substrate in the same manner as in Example 14 except that the sputtering target was replaced with a target of a sintered boded formed of a hexagonal laminar compound of In 2 O 3 (ZnO) 4 , and indium oxide (In 2 O 3 ) in which the atomic ratio of In, In/(In+Zn), was 0.75.
  • ZnO hexagonal laminar compound of In 2 O 3
  • In 2 O 3 indium oxide
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.79. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive layer II having a thickness of 200 nm was formed on a transparent polymer substrate in the same manner as in Example 12 except that the sputtering target was replaced with a target of a sintered body formed of a compound prepared by incorporating tin oxide into a hexagonal laminar compound of In 2 O 3 (ZnO) 4 in which the atomic ratio of In, In/(In+Zn), was 0.75 and the atomic ratio of Sn as a third element, Sn/(In+Zn+Sn) was 0.04.
  • the transparent electrically conductive layer II was formed of a composition formed by incorporating an oxide of Sn into a composition of indium oxide and zinc oxide, and it was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.78 and that the atomic ratio of Sn, Sn/(In+Zn+Sn) was 0.04. Further, the transparent electrically conductive layer II was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer II was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer II was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive layer having a thickness of 300 nm was formed on a transparent polymer substrate in the same manner as in Example 9 except that the sputtering target was replaced with a sputtering target of a sintered body formed of a compound (ITO) of indium oxide and tin oxide in which the atomic ratio of In to Sn, In/Sn, was 9/1 and that the substrate temperature in forming the film was set at 80° C.
  • ITO compound
  • the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show a sharp peak of In 2 O 3 .
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive film having a thickness of 200 nm was formed on a transparent polymer substrate in the same manner as in Example 12 except that the sputtering target was replaced with a sputtering target of a sintered body formed of a compound (ITO) of indium oxide and tin oxide in which the atomic ratio of In to Sn, In/Sn, was 9/1.
  • ITO indium oxide
  • tin oxide in which the atomic ratio of In to Sn, In/Sn
  • the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show a slight peak of In 2 O 3 .
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive film was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive layer having a thickness of 200 nm was formed on a transparent polymer substrate in the same manner as in Example 12 except that the sputtering target was replaced with a target of indium oxide containing zinc oxide (sintered body in which atomic ratio of In, In/(In+Zn), was 0.90).
  • the transparent electrically conductive layer was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.93. Further, the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive layer having a thickness of 200 nm was formed on a transparent polymer substrate in the same manner as in Example 12 except that the sputtering target was replaced with a target of indium oxide containing zinc oxide (sintered body in which atomic ratio of In, In/(In+Zn), was 0.93).
  • the transparent electrically conductive layer was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.97. Further, the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive layer having a thickness of 200 nm was formed on a transparent polymer substrate in the same manner as in Example 16 except that the sputtering target was replaced with a target of indium oxide containing zinc oxide (sintered body in which atomic ratio of In, In/(In+Zn), was 0.93).
  • the transparent electrically conductive layer was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.97. Further, the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show a slight peak of In 2 O 3 .
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • a transparent electrically conductive layer having a thickness of 200 nm was formed on a transparent polymer substrate in the same manner as in Example 12 except that the sputtering target was replaced with a target prepared by arranging three indium oxide tablets (diameter 10 mm, thickness 5 mm) on a zinc oxide disk having a diameter of 4 inches.
  • the transparent electrically conductive layer was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.12. Further, the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • An epoxy resin (epoxy acrylate) layer having a thickness of 1 ⁇ m was formed on a transparent polymer substrate by a spin coating method, and the epoxy resin was crosslinked by exposing it to UV to form a crosslinked resin layer. Thereafter, a transparent electrically conductive layer I having a thickness of 200 nm was formed on the above crosslinked resin layer in the same manner as in Example 12.
  • the transparent electrically conductive layer was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.70. Further, the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 3 shows the results.
  • the electrically conductive transparent films obtained in Examples 9 to 18 had practically sufficient electrical conductivity and light transmittance.
  • the surface resistance (specific resistance) of each electrically conductive transparent film tested on resistance to moist heat showed only a small change from the surface resistance which each showed before the test on resistance to moist heat, so that it is seen that each electrically conductive transparent film was excellent in resistance to moist heat.
  • the transparent electrically conductive layers (transparent electrically conductive layers I or II) constituting the electrically conductive transparent films obtained in Examples 9 to 18 had high etching rates, so that it is seen that the transparent electrically conductive layers were excellent in etching properties.
  • the electrically conductive transparent film of Comparative Example 9 in which a crystalline ITO layer was formed as a transparent electrically conductive layer had practically sufficient electrical conductivity and light transmittance, while the surface resistance after the test on resistance to moist heat showed a great change from the surface resistance before the test. It is therefore seen that the electrically conductive transparent film of Comparative Example 9 was poor in resistance to moist heat. Further, the transparent electrically conductive layer (ITO layer) constituting the electrically conductive transparent film showed a low etching rate. This is also true of the electrically conductive transparent film of Comparative Example 10 in which a crystalline ITO layer was formed as a transparent electrically conductive layer. Further, those in Comparative Examples 11 and 12 had excellent resistance to moist heat, while they were inferior to those in Examples 9 to 18 in electrical conductivity and etching properties (etching rate). And, those in Comparative Examples 13 and 14 had low electrical conductivity.
  • An alkali-free glass sheet having a thickness of 125 ⁇ m was used as a transparent glass substrate and a sintered body formed of a composition containing indium oxide and zinc oxide in which the atomic ratio of In, In/(In+Zn) was 0.67 was used as a sputtering target for producing an electrically conductive transparent glass in the following manner.
  • the voltage to be applied to the target was set at 420 V
  • the substrate temperature was set at 240° C.
  • a transparent electrically conductive layer I having a thickness of 310 nm was formed on the transparent glass substrate by DC magnetron direct sputtering.
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn) was the same as that of the sputtering target, or 0.67. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous. The result of the X-ray diffraction measurement was substantially the same as that shown in FIG. 1.
  • the above electrically conductive transparent glass was measured for a light transmittance
  • the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9.
  • the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9.
  • the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9.
  • the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • An alkali-free glass sheet having a thickness of 125 ⁇ m was used as a transparent glass substrate and a target formed of an alloy of indium and zinc in which the atomic ratio of In, In/(In+Zn) was 0.67 was used as a sputtering target for producing an electrically conductive transparent glass in the following manner.
  • the voltage to be applied to the target was set at 420 V
  • the substrate temperature was set at 240° C.
  • a transparent electrically conductive layer I having a thickness of 280 nm was formed on the transparent glass substrate by reactive sputtering.
  • the transparent electrically conductive layer I was formed of a composition containing indium oxide and zinc oxide, and it was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn) was 0.67. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent glass was measured for a light transmittance
  • the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9.
  • the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9.
  • the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9.
  • the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • An alkali-free glass sheet having a thickness of 125 ⁇ m was used as a transparent glass substrate, and a sintered body formed of a composition prepared by incorporating tin oxide into a composition containing indium and zinc in which the atomic ratio of In, In/(In+Zn) was 0.67 and the atomic ratio of Sn as a third element, Sn/(In+Zn+Sn) was 0.04, was used as a sputtering target for producing an electrically conductive transparent glass in the following manner.
  • the voltage to be applied to the target was set at 350 V
  • the substrate temperature was set at 210° C.
  • a transparent electrically conductive layer II having a thickness of 300 nm was formed on the transparent glass substrate by DC magnetron direct sputtering.
  • the transparent electrically conductive layer II was formed of a composition obtained by incorporating an oxide of Sn into the composition containing indium oxide and zinc oxide, and it was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn) was 0.67 and that the atomic ratio of Sn as a third element, Sn/(In+Zn+Sn) was 0.04. Further, the transparent electrically conductive layer II was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent film was measured for a light transmittance, and the above transparent electrically conductive layer II was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent film was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer II was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • the sputtering output was set at 100 W
  • the substrate temperature was set at 20° C.
  • a transparent electrically conductive film I having a thickness of 200 nm was formed on the transparent glass substrate by RF magnetron direct sputtering.
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.70. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent glass was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent glass was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • a transparent electrically conductive layer I having a thickness of 200 nm was formed on a transparent glass substrate in the same manner as in Example 22 except that the sputtering target was replaced with a target of a sintered body formed of a hexagonal laminar compound of In 2 O 3 (ZnO) 4 , and indium oxide (In 2 O 3 ) in which the atomic ratio of In, In/(In+Zn), was 0.70.
  • ZnO hexagonal laminar compound of In 2 O 3
  • In 2 O 3 indium oxide
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.74. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent glass was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent glass was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • a transparent electrically conductive layer I having a thickness of 250 nm was formed on a transparent glass substrate in the same manner as in Example 24 except that the substrate temperature in forming the film was set at 200° C.
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.73. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent glass was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent glass was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same! manner as in Example 9. Further, the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • a transparent electrically conductive layer I having a thickness of 250 nm was formed on a transparent glass substrate in the same manner as in Example 24 except that the RF magnetron direct sputtering apparatus was replaced with a D(C magnetron direct sputtering apparatus.
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.73. Further, the transparent electrically conductive layer I was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • Example 9 the above electrically conductive transparent glass was measured for a light transmittance, and the above transparent electrically conductive layer I was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent glass was tested for a resistance to moist heat in the same manner as in. Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer I was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • a transparent electrically conductive layer I having a thickness of 200 nm was formed on a transparent glass substrate in the same manner as in Example 23 except that the sputtering target was replaced with a target prepared by arranging five zinc oxide tablets (diameter 10 mm, thickness 5 mm) on an indium oxide disk having a diameter of 4 inches.
  • the transparent electrically conductive layer I was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.72. Further, the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent layer was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent glass was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • a transparent electrically conductive layer having a thickness of 350 nm was formed on a transparent glass substrate in the same manner as in Example 20 except that the sputtering target was replaced with a sputtering target of a sintered body formed of a compound (ITO) of indium oxide and tin oxide in which the atomic ratio of In to Sn, In/Sn, was 9/1.
  • ITO indium oxide
  • tin oxide in which the atomic ratio of In to Sn, In/Sn
  • the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show a sharp peak of In 2 O 3 .
  • the above electrically conductive transparent glass was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent glass was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • a transparent electrically conductive layer having a thickness of 200 nm was formed on a transparent glass substrate in the same manner as in Example 23 except that the sputtering target was replaced with a sputtering target of a sintered body formed of a compound (ITO) of indium oxide and tin oxide in which the atomic ratio of In to Sn, In/Sn, was 9/1.
  • ITO indium oxide
  • tin oxide in which the atomic ratio of In to Sn, In/Sn
  • the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show a slight peak of In 2 O 3 .
  • the above electrically conductive transparent glass was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent glass was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • a transparent electrically conductive layer having a thickness of 250 nm was formed on a transparent glass substrate in the same manner as in Example 23 except that the sputtering target was replaced with a target of indium oxide containing zinc oxide (sintered body in which atomic ratio of In, In/(In+Zn), was 0.90).
  • the transparent electrically conductive layer was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.93. Further, the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent: glass was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent glass was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • a transparent electrically conductive layer having a thickness of 250 nm was formed on a transparent glass substrate in the same manner as in Example 25 except that the sputtering target was replaced with a target of indium oxide containing zinc oxide (sintered body in which atomic ratio of In, In/(In+Zn), was 0.90).
  • the transparent electrically conductive film was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.93. Further, the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent glass was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent glass was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • a transparent electrically conductive layer having a thickness of 250 nm was formed on a transparent glass substrate in the same manner as in Example 26 except that the sputtering target was replaced with a target of indium oxide containing zinc oxide (sintered body in which atomic ratio of In, In/(In+Zn), was 0.93).
  • the transparent electrically conductive layer was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.97. Further, the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent glass was measured for a light transmittance, and the above transparent electrically conductive film was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent glass was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • a transparent electrically conductive layer having a thickness of 220 nm was formed on a transparent glass substrate in the same manner as in Example 23 except that the sputtering target was replaced with a target prepared by arranging three indium oxide tablets (diameter 10 mm, thickness 5 mm) on a zinc oxide disk having a diameter of 4 inches.
  • the transparent electrically conductive layer was measured for a composition by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.12. Further, the transparent electrically conductive layer was analyzed for crystallizability by X-ray diffraction to show that it was amorphous.
  • the above electrically conductive transparent glass was measured for a light transmittance, and the above transparent electrically conductive layer was measured for a surface resistance, in the same manner as in Example 9. Further, the electrically conductive transparent glass was tested for a resistance to moist heat in the same manner as in Example 9. Then, the surface resistance and the light transmittance after a test time of 1,000 hours were measured in the same manner as in Example 9. Further, the transparent electrically conductive layer was measured for an etching rate in the same manner as in Example 9. Table 4 shows the results.
  • the electrically conductive transparent glass of Comparative Example 15 in which a crystalline ITO layer was formed as a transparent electrically conductive layer was excellent in electrical conductivity, light transmittance and resistance to moist heat, while the etching rate of the crystalline ITO layer constituting the electrically conductive transparent glass was far lower than those of the layers in Examples 20 to 27.
  • the electrically conductive transparent glass of Comparative Example 16 in which the crystallite ITO layer was formed as a transparent electrically conductive layer was superior to the glass of Comparative Example 15 in the etching properties (etching rate) of transparent electrically conductive layer, while the etching rate of the ITO layer in Comparative Example 16 was still lower than those of the layers in Examples 20 to 27.
  • Comparative Example 16 was also inferior to those of Examples 20 to 27 in resistance to moist heat.
  • Those of Comparative Examples 17 and 19 had practically sufficient electrical conductivity and light transmittance, and had excellent resistance to moist heat, while they were inferior to those of Examples 20 to 27 in etching properties (etching rate). Further, those of Comparative Examples 18 and 20 had low electrical conductivity.
  • a biaxially oriented polyester film having a thickness of 100 ⁇ m was used as a transparent polymer substrate and a target prepared by placing three sintered bodies of ZnO (diameter 10 mm, thickness 5 mm, relative density 80%) on a sintered body of In 2 O 3 (diameter 4 inches, thickness 5 mm, relative density 73%) was used as a sputtering target for forming a transparent electrically conductive layer I on the above polyester film in the following manner.
  • the above transparent electrically conductive layer I having a thickness of 273 nm was formed on the above polyester film under the conditions where the RF output was 1.2 W/cm 2 and the substrate temperature was 20° C.
  • the so-obtained transparent electrically conductive layer I was measured by X-ray diffraction to show that it was amorphous. Further, the transparent electrically conductive layer I was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.88.
  • the above transparent electrically conductive layer I was measured for a surface resistance and a light transmittance (wavelength of test light: 550 nm), and also measured for an etching rate in the same manner as in Example 9. Further, the specific resistance thereof was calculated. Table 5 shows the results.
  • An alkali-free glass plate (#7059, supplied by Corning) was used as a transparent glass substrate, and a transparent electrically conductive layer I having a thickness of 200 nm was formed on the above glass plate under the same conditions as those in Example 28.
  • the so-obtained transparent electrically conductive layer I was measured by X-ray diffraction to show that it was amorphous. Further, the transparent electrically conductive layer I was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.88.
  • the above transparent electrically conductive layer I was measured for a surface resistance, a light transmittance and an etching rate in the same manner as in Example 28. Further, the transparent electrically conductive layer I was heated at 200° C. for 1 hour, and then measured for a surface resistance. Further, the specific resistance values of the transparent electrically conductive layer I before and after the heating were calculated. Table 5 shows the results.
  • a transparent electrically conductive layer I having a thickness of 100 nm was formed on the same glass plate as that used in Example 29 under the same conditions as those in Example 29 except that the substrate temperature was set at 2000° C.
  • the so-obtained transparent electrically conductive layer I was measured by X-ray diffraction to show that it was amorphous. Further, the transparent electrically conductive layer I was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.88.
  • the above transparent electrically conductive layer I was measured for a surface resistance, a light transmittance and an etching rate in the same manner as in Example 28. Further, the transparent electrically conductive layer I was heated at 200° C. for 1 hour, and then measured for a surface resistance. Further, the specific resistance values of the transparent electrically conductive layer I before and after the heating were calculated. Table 5 shows the results.
  • ZnO hexagonal laminar compound of In 2 O 3
  • the so-obtained transparent electrically conductive layer I was measured by X-ray diffraction to show that it was amorphous. Further, the transparent electrically conductive layer I was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.88.
  • the above transparent electrically conductive layer I was measured for a surface resistance, a light transmittance and an etching rate in the same manner as in Example 28. Further, the specific resistance thereof was calculated. Table 5 shows the results.
  • An alkali-free glass plate (#7059, supplied by Corning) was used as a transparent glass substrate, and a transparent electrically conductive layer I having a thickness of 250 nm was formed on the above glass plate under the same conditions as those in Example 31.
  • the so-obtained transparent electrically conductive layer I was measured by X-ray diffraction to show that it was amorphous. Further, the transparent electrically conductive layer I was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.87.
  • the above transparent electrically conductive layer I was measured for a surface resistance, a light transmittance and an etching rate in the same manner as in Example 28. Further, the transparent electrically conductive layer I was heated at 200° C. for 1 hour, and then measured for a surface resistance. Further, the specific resistance values of the transparent electrically conductive layer I before and after the heating were calculated. Table 5 shows the results.
  • ZnO hexagonal laminar compound of In 2 O 3
  • the so-obtained transparent electrically conductive layer I was measured by X-ray diffraction to show that it was amorphous. Further, the transparent electrically conductive layer I was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.84.
  • the above transparent electrically conductive layer I was measured for a surface resistance, a light transmittance and an etching rate in the same manner as in Example 28. Further, the transparent electrically conductive layer I was heated at 200° C. for 1 hour, and then measured for a surface resistance. Further, the specific resistance values of the transparent electrically conductive layer I before and after the heating were calculated. Table 5 shows the results.
  • ZnO hexagonal laminar compound of In 2 O 3
  • In 2 O 3 In 2 O 3
  • the so-obtained transparent electrically conductive layer II was measured by X-ray diffraction to show that it was amorphous. Further, the transparent electrically conductive layer II was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.87 and that the atomic ratio of. Sn, Sn/(In+Zn+Sn) was 0.02.
  • the above transparent electrically conductive layer II was measured for a surface resistance, a light transmittance and an etching rate in the same manner as in Example 23. Further, the transparent electrically conductive layer II was heated at 200° C. for 1 hour, and then measured for a surface resistance. Further, the specific resistance values of the transparent electrically conductive layer II before and after the heating were calculated. Table 5 shows the results.
  • the so-obtained transparent electrically conductive layer was measured by X-ray diffraction to show that it was amorphous. Further, the transparent electrically conductive layer was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was outside the range defined by the present invention, or 0.93.
  • the above transparent electrically conductive layer was measured for a surface resistance, a light transmittance and an etching rate in the same manner as in Example 28. Further, the transparent electrically conductive layer was heated at 200° C. for 1 hour, and then measured for a surface resistance. Further, the specific resistance values of the transparent electrically conductive layer before and after the heating were calculated. Table 5 shows the results.
  • a transparent electrically conductive layer having a thickness of 100 nm was formed on the same glass plate as above under the same conditions as those in Example 30 except that the sputtering target was replaced with a target of ITO (In 2 O 3 --5 wt % SnO 2 ).
  • the so-obtained transparent electrically conductive layer was measured by X-ray diffraction to show a crystal of indium oxide.
  • the above transparent electrically conductive layer was measured for a surface resistance, a light transmittance and an etching rate in the same manner as in Example 1. Table 5 shows the results.
  • An epoxy resin (epoxy acrylate) layer having a thickness of 1pm was formed on a transparent polymer substrate by a spin coating method, and the epoxy resin was crosslinked by exposing it to UV to form a crosslinked resin layer. Thereafter, a transparent electrically conductive layer I having a thickness of 200nm was formed on the above crosslinked resin layer in the same manner as in Example 33.
  • the so-obtained transparent electrically conductive layer I was measured by X-ray diffraction to show that it was amorphous. Further, the transparent electrically conductive layer I was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.84.
  • the above transparent electrically conductive layer I was measured for a surface resistance, a light transmittance and an etching rate in the same manner as in Example 28. Further, the specific resistance thereof was calculated. Table 5 shows the results.
  • the transparent electrically conductive layers obtained in Examples 28 to 35 not only had practically sufficient electrical conductivity and transparency, but also had excellent etching properties. Further, as is clear from the specific resistance values calculated before and after the heat treatment, it is seen that the transparent electrically conductive layers obtained in Examples 29, 30, 32, 33, 34 and 35 were excellent in thermal stability of specific resistance. Meanwhile, the transparent electrically conductive layers obtained in Examples 28, 31 and 35 had not been heat-treated for making sure the thermal stability of specific resistance since the substrates therefor had low heat resistance. However, the transparent electrically conductive layer obtained in Example 28 was quality-wise substantially identical with the transparent electrically conductive layer obtained in Example 29.
  • the transparent electrically conductive layer obtained in Example 31 was quality-wise substantially identical with the transparent electrically conductive layer obtained in Example 32. Further, the transparent electrically conductive layer obtained in Example 35 was quality-wise substantially identical with the transparent electrically conductive layer obtained in Example 33. It can be therefore considered that the transparent electrically conductive layers obtained in Examples 28, 31 and 35 were also excellent in thermal stability of specific resistance.
  • the transparent electrically conductive layer of Comparative Example 21 in which the atomic ratio of In, In/(In+Zn), was outside the range defined by the present invention, had practically sufficient electrical conductivity and transparency and had excellent etching properties, while it had very low thermal stability of specific resistance. Further, the crystalline transparent electrically conductive layer obtained in Comparative Example 22 using the target of ITO was excellent in electrical conductivity and transparency, while it was inferior to the transparent electrically conductive layers of Examples 28 to 35 in etching properties.
  • the above-obtained aqueous solution and the above-obtained alkaline aqueous solution were simultaneously added dropwise to a container containing 100 cc of ion-exchanged water and having a volume of 5 liters, with vigorously stirring at a room temperature, to allow these two solutions to react.
  • the rate of the above addition was adjusted such that the reaction system maintained a pH of 9.0.
  • the mixture was further stirred for 1 hour.
  • the above aqueous solution and the above alkaline aqueous solution were allowed to react as described above, to form a precipitate, and a slurry was obtained.
  • the concentration of the total amount of In and Zn in the reaction system was 0.3 mol/liter.
  • the above-obtained slurry was fully washed with water, and the precipitate was recovered by filtration.
  • the recovered precipitate was dried at 120° C. overnight, and fired at 900° C. for 5 hours.
  • the above-obtained fired product was placed in a pot formed of polyamide having a volume of 80 cc, together with alumina balls having a diameter of 2 mm, and ethanol was added.
  • the fired product was pulverized with a planetary ball mill for 2 hours.
  • the so-obtained powder was measured by X-ray diffraction to show the formation of a hexagonal laminar compound of In 2 O 3 (ZnO) 3 , and its content was 60 wt %. Further, the powder was substantially homogeneous as a composition.
  • the content of the hexagonal laminar compound was quantitatively determined with a powder X-ray diffraction apparatus according to the method described in "Ceramics Characterization Technique" (issued by Corporation of Ceramic Industry Society, 1987, pages 44-45) (The same measurement was carried out in Examples to be described below). Further, the powder was analyzed for a composition with XMA (X-ray microanalyzer).
  • the above-obtained powder was observed through an SEM (scanning electron microscope) to show that it had an average particle diameter of 0.12 ⁇ m and that the diameters thereof were substantially uniform.
  • the above-obtained powder had a volume solid resistivity of 950 ⁇ cm.
  • the powder showed a volume solid resistivity of as low as 1,000 ⁇ cm even after a 1,000 hours' test on resistance to moist heat under the conditions of 40° C. and 90 % RH, which shows that the powder was excellent in resistance to moist heat.
  • the above "volume solid resistivity" (sometimes referred to as "powder resistivity”) was determined by placing 1 g of a sample in a cylinder formed of a resin having an internal diameter of 10 mm, applying a pressure at 100 kg/cm 2 , measuring a resistance with a tester and substituting measurement values in the following equation (the same determination was carried out in Examples to be described below). ##EQU1## (2) Preparation of Electrically Conductive Material I (sintered body)
  • the powder obtained in the above (1) was placed in a 10 mm ⁇ mold, and preliminarily shaped with a press molding machine at a pressure of 100 kg/cm 2 . Then, the shaped body was compressed with a cold isostatic press molding machine at a pressure of 4 t/cm 2 , and sintered at 1,300° C. for 5 hours to give a sintered body.
  • the so-obtained sintered body was found to contain 80 wt % of a hexagonal laminar compound of In 2 O 3 (ZnO) 3 , and the composition and particle diameters thereof were substantially uniform.
  • the sintered body had a relative density of 95%.
  • the so-obtained powder was measured by X-ray diffraction to show the formation of a hexagonal laminar compound of In 2 O 3 (ZnO) 5 , and its content was 60 wt %. Further, the powder was substantially homogeneous as a composition. The powder was observed through an SEM to show that it had an average particle diameter of 0.20 ⁇ m and that the diameters thereof were substantially uniform.
  • the above-obtained powder had a volume solid resistivity of 700 ⁇ cm.
  • the powder showed a volume solid resistivity of as low as 730 ⁇ cm even after a 1,000 hours' test on resistance to moist heat under the conditions of 40° C. and 90 % RH, which shows that the powder was excellent in resistance to moist heat.
  • the powder obtained in the above (1) was preliminarily shaped, and the shaped body was compressed, in the same manner as in Example 36(2), and the shaped body was sintered at 1,350° C. for 5 hours to give a sintered body.
  • the so-obtained sintered body was found to be formed of a hexagonal laminar compound of In 2 O 3 (ZnO), and the composition and particle diameters thereof were substantially uniform.
  • the sintered body had a relative density of 96%.
  • Example 37(1) An aqueous solution containing indium salt and zinc salt was prepared in the same manner as in Example 37(1), and then 7.2 g (5 at %) of stannic chloride was added to the aqueous solution.
  • This aqueous solution and an alkaline aqueous solution prepared in the same manner as in Example 36(1) were allowed to react in the same manner as in Example 36(1) to give a slurry.
  • the so-obtained powder was measured by X-ray diffraction to show the formation of 60 wt % of In 2 O 3 (ZnO) 5 .
  • the above powder had a volume solid resistivity of 330 ⁇ cm.
  • the powder had a volume solid resistivity of as low as 350 ⁇ cm even after a 1,000 hours' test on resistance to moist heat under the conditions of 40° C. and 90% RH, which shows that the powder was excellent in resistance to moist heat.
  • the powder obtained in the above (1) was preliminarily shaped, and the shaped body was compressed, in the same manner as in Example 36(2), and the shaped body was sintered at 1,350° C. for 5 hours to give a sintered body.
  • the so-obtained sintered body was found to be a hexagonal laminar compound of In 2 O 3 (ZnO) 5 in an amount of 80 wt %, and the particle diameters thereof were substantially uniform.
  • the sintered body had a relative density of 95%.
  • the so-obtained powder was placed in a mold having a diameter of 4 inches, and preliminarily shaped with a press molding machine at a pressure of 100 kg/cm 2 . Then, the shaped body was compressed with a cold isostatic press molding machine at a pressure of 4 t/cm 2 , and fired by hot isostatic pressing at 1,000 kgf/cm 2 at 1,300° C. for 3 hours to give a sintered body.
  • the so-obtained sintered body was measured by X-ray diffraction to show that it was a hexagonal laminar compound of In 2 O 3 (ZnO) 4 .
  • the so-obtained sintered body was analyzed by ICP (inductively coupled plasma atomic emission spectrochemical analysis) using SPS-1500VR supplied by Seiko Instruments Inc. to show that the atomic ratio of In, In/(In+Zn), was 0.33. Further, the sintered body had a relative density of 88%.
  • the so-obtained powder was placed in a mold having a diameter of 4 inches, and preliminarily shaped with a press molding machine at a pressure of 100 kg/cm 2 . Then, the shaped body was compressed with a cold isostatic press molding machine at a pressure of 4 t/cm 2 , and fired by hot isostatic pressing at 1,500 kgf/cm 2 at 1,450° C. for 3 hours to give a sintered body.
  • the so-obtained sintered body was measured by X-ray diffraction to show that it was a mixture of a hexagonal laminar compound of In 2 O 3 (ZnO) 5 , and In 2 O 3 .
  • the so-obtained sintered body was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.50. Further, the sintered body had a relative density of 93%.
  • the pulverizing, mixing, calcining, molding and sintering were carried out in the same manner as in Example 40 except that 300 g of indium oxide and 80 g of zinc oxide were used.
  • the so-obtained sintered body was measured by X-ray diffraction to show that it was a mixture of a hexagonal laminar compound of In 2 O 3 (ZnO) 3 , and In 2 O 3 .
  • the so-obtained sintered body was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.67. Further, the sintered body had a relative density of 92%.
  • the pulverizing, mixing, calcining, molding and sintering were carried out in the same manner as in Example 40 except that 278 g of indium oxide and 52 g of zinc oxide were used.
  • the so-obtained sintered body was measured by X-ray diffraction to show that it was a mixture of a hexagonal laminar compound of In 2 O 3 (ZnO) 3 , and In 2 O 3 .
  • the so-obtained sintered body was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.75. Further, the sintered body had a relative density of 96%.
  • the pulverizing, mixing, calcining, molding and sintering were carried out in the same manner as in Example 40 except that 278 g of indium oxide and 38 g of zinc oxide were used.
  • the so-obtained sintered body was measured by X-ray diffraction to show that it was a mixture of a hexagonal laminar compound of In 2 O 3 (ZnO) 3 , and In 2 O 3 .
  • the so-obtained sintered body was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.80. Further, the sintered body had a relative density of 95%.
  • the pulverizing, mixing, calcining and molding were carried out in the same manner as in Example 40 except that 278 g of indium oxide and 38 g of zinc oxide were used.
  • the molded body was sintered by hot isostatic pressing at 1,000 kgf/cm 2 at 1,200° C. for 3 hours.
  • the resultant sintered body was measured by X-ray diffraction to show that it was a mixture of a hexagonal laminar compound of In 2 O 3 (ZnO) 5 , and In 2 O 3 .
  • the so-obtained sintered body was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.80. Further, the sintered body had a relative density of 82%.
  • the pulverizing, mixing, calcining, molding and sintering were carried out in the same manner as in Example 40 except that 278 g of indium oxide and 27.5 g of zinc oxide were used.
  • the resultant sintered body was measured by X-ray diffraction to show that it was a mixture of a hexagonal laminar compound of In 2 O 3 (ZnO) 3 , and In 2 O 3 .
  • the so-obtained sintered body was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.85%. Further, the sintered body had a relative density of 95%.
  • the powder obtained in the above (1) was placed in a mold having a diameter of 4 inches, and preliminarily shaped with a press molding machine at a pressure of 100 kg/cm 2 . Then, the shaped body was compressed with a cold isostatic press molding machine at a pressure of 4 t/cm 2 , and fired by hot isostatic pressing at 1,500 kgf/cm 2 at 1,450° C. for 3 hours.
  • the resultant sintered body was measured by X-ray diffraction to show that it was a mixture of a hexagonal laminar compound of In 2 O 3 (ZnO) 4 , and In 2 O 3 .
  • the so-obtained sintered body was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.85. Further, the sintered body had a relative density of 95%.
  • the pulverizing, mixing, calcining, molding and sintering were carried out in the same manner as in Example 45 except that 5 at % of Sn was added as a third element.
  • the resultant sintered body was measured by X-ray diffraction to show that it was a mixture of a hexagonal laminar compound of In 2 O 3 (ZnO) 3 , and In 2 O 3 .
  • the so-obtained sintered body was analyzed by ICP to show that the atomic ratio of In, In/(In+Zn), was 0.85 and that the atomic ratio of Sn, Sn/(In+Zn+Sn), was 0.05. Further, the sintered body had a relative density of 92%.
  • the so-obtained powder was measured by X-ray diffraction to show the formation of 70 wt % of In 2 O 3 (ZnO) 5 . Further, the powder was measured for a volume solid resistivity to show 25 ⁇ cm. The powder still showed a volume solid resistivity of 32 ⁇ cm after a 1,000 hours' test on humidity resistance under the conditions of 40° C. and 90% RH, which shows that the powder was excellent in humidity resistance. The powder was also analyzed with SEM and XMA to show that it had an average particle diameter of 0.22 ⁇ m and had a homogeneous composition.
  • Polyvinyl alcohol in an amount of 2 wt % was added to the powder obtained in the above (1), and the mixture was press-shaped at 100 kg/cm 2 in a mold having a diameter of 150 mm. Further, the shaped body was compressed by cold isostatic pressing at 4 t/cm 2 .
  • the so-obtained shaped body was decreased at 500° C. for 10 minutes, and then sintered at 1,200° C. for 4 hours.
  • the so-obtained sintered body was measured by X-ray diffraction to show the formation of 90 wt % of In 2 O 3 (ZnO) 5 .
  • This sintered body had a density of 92% and a volume resistivity of 5 ⁇ 10 -3 ⁇ cm.
  • a yellowish powder was obtained from the solution A and the solution B in the same manner as in Example 48(1).
  • the powder was measured by X-ray diffraction to show the formation of 60 wt % of In 2 O 3 (ZnO) 3 . Further, the powder was measured for a volume solid resistivity to show 18 ⁇ cm. The powder still showed a volume resistivity of 25 ⁇ cm after a 1,000 hours' test on humidity resistance under the conditions of 40° C. and 90% RH, which shows that the powder was excellent in humidity resistance.
  • the powder was also analyzed with SEM and XMA to show that it had an average particle diameter of 0.15 ⁇ m and had a homogeneous composition.
  • the powder obtained in the above (1) was treated in the same manner as in Example 48(2) to give a sintered body.
  • the sintered body was measured by X-ray diffraction to show the formation of 80 wt % of In 2 O 3 (ZnO) 3 .
  • This sintered body had a density of 93% and a volume resistivity of 2 ⁇ 10 -3 ⁇ cm.
  • a powder was prepared from the above solutions A and B in the same manner as in Example 48(1). This powder was also yellowish.
  • the powder was measured by X-ray diffraction to show the formation of 60 wt % of In 2 O 3 (ZnO) 5 . Further, the powder was measured for a volume solid resistivity to show 15 ⁇ cm. The powder still showed a volume solid resistivity of 19 ⁇ cm after a 1,000 hours' test on humidity resistance under the conditions of 40° C. and 90% RH, which shows that the powder was excellent in humidity resistance. The powder was also analyzed with SEM and XMA to show that it had an average particle diameter of 0.21 ⁇ m and had a homogeneous composition.
  • a sintered body was obtained from the powder obtained in the above (1), in the same manner as in Example 18(2).
  • the sintered body was measured by X-ray diffraction to show the formation of 80 wt % of In 2 O 3 (ZnO) 5 . Further, the sintered body had a density of 91% and a volume resistivity of 1 ⁇ 10.sup. ⁇ ⁇ cm.
  • the above-obtained aqueous solution and the above-obtained alkaline aqueous solution were simultaneously added dropwise to a container containing 100 cc of ion-exchanged water and having a volume of 5 liters, with vigorously stirring at a room temperature, to allow these two solutions to react.
  • the rate of the above addition was adjusted such that the reaction system maintained a pH of 9.0.
  • the mixture was further stirred. for 1 hour.
  • the above aqueous solution and the above alkaline aqueous solution were allowed to react as described above, to form a precipitate, and a slurry was obtained.
  • the concentration of the total amount of In and Zn in the reaction system was 0.32 mol/liter.
  • the above-obtained dry product was fired at 600° C. for 5 hours, and then placed in a pot formed of polyamide having a volume of 80 cc, together with alumina balls having a diameter of 2 mm, and ethanol was added.
  • the above product was pulverized with a planetary ball mill for 2 hours to give a powder.
  • the so-obtained powder was measured by X-ray diffraction to show that 60 wt % of the powder was amorphous content, and it was also analyzed for a composition to show that the atomic ratio of In, In/(In+Zn), was 0.66.
  • the powder was substantially homogeneous as a composition. This powder comes under the electrically conductive material III.
  • the content of a crystalline substance was quantitatively determined with a powder X-ray diffraction apparatus according to the method described in "Ceramics Characterization Technique" (issued by Corporation of Ceramic Industry Society, 1987, pages 44-45), and the remainder was taken as the amorphous oxide (The measurement in Examples to be described below was carried out in this manner).
  • the above-obtained powder was observed through an SEM (scanning electron microscope) to show that it had an average particle diameter of 0.15 ⁇ m and that the diameters thereof were substantially uniform.
  • the above-obtained powder had a volume solid resistivity of 100 ⁇ cm.
  • the powder showed a volume solid resistivity of as low as 105 ⁇ cm even after a 1,000 hours' test on humidity resistance under the conditions of 40° C. and 90% RH (relative humidity), which shows that the powder was excellent in humidity resistance.
  • Example 2 Thereafter, the above-obtained dry product was fired at 500° C. for 5 hours, and then the fired product was pulverized in the same manner as in Example 1 to give a powder.
  • the so-obtained powder was measured by X-ray diffraction to show that 70 wt % of the powder was amorphous content, and it was also analyzed for a composition to show that the atomic ratio of In, In/(In+Zn), was 0.33.
  • the powder was substantially homogeneous as a composition. This powder comes under the electrically conductive material III.
  • the above-obtained powder was observed through an SEM to show that it had an average particle diameter of 0.23 ⁇ m and that the diameters thereof were substantially uniform.
  • the above-obtained powder had a volume solid resistivity of 550 ⁇ cm.
  • the powder showed a volume solid resistivity of as low as 560 ⁇ cm even after a 1,000 hours' test on humidity resistance under the conditions of 40° C. and 90% RH (relative humidity), which shows that the powder was excellent in humidity resistance.
  • Example 51 An aqueous solution containing metal salts of indium and zinc was prepared in the same manner as in Example 51, and 7.7 g (5 at %) of cupric chloride was further added.
  • the aqueous resultant solution and an alkaline aqueous solution prepared in the same manner as in Example 51 were allowed to react in the same manner as in Example 51 to give a slurry.
  • the above-obtained slurry was fully washed with water, and then a precipitate was recovered by filtration.
  • the recovered precipitate was dried at 120° C., and fired at 600° C. for 5 hours.
  • the resultant product was placed in a pot formed of polyamide having a volume of 80 cc, together with ball mill, and ethanol was added.
  • the above product was pulverized with a planetary ball mill for 2 hours.
  • Example 51 the resultant fired product was pulverized in the same manner as in Example 51 to give a powder.
  • the so-obtained powder was measured by X-ray diffraction to show that 60 wt % of the powder was amorphous content.
  • the powder was substantially homogeneous as a composition. This powder comes under the electrically conductive material III.
  • the above-obtained powder had a volume solid resistivity of 90 ⁇ cm.
  • the powder showed a volume solid resistivity of as low as 100 ⁇ cm even after a 1,000 hours' test on humidity resistance under the conditions of 40° C. and 90% RH, which shows that the powder was excellent in humidity resistance.
  • the resultant product was pulverized with a ball mill (20 hours), and then resultant powder was reduction-treated under vacuum at 200° C. for 2 hours to give a yellowish powder.
  • the so-obtained powder was measured by X-ray diffraction to show that 90 wt % of the powder was amorphous or that the powder was substantially amorphous. Further, the powder was analyzed for a composition to show that the atomic ratio of In, In/(In+Zn), was 0.67. This powder comes under the electrically conductive material III.
  • the above powder was measured for a volume solid resistivity to show 5 ⁇ cm.
  • the powder still showed a volume solid resistivity of 6 ⁇ cm or showed almost no change after a 1,000 hours' test on humidity resistance under the conditions of 40° C. and 90% RH, which shows that the powder was excellent in humidity resistance.
  • the powder was also analyzed with SEM and KMA to show that it had an average particle diameter of 0.20 ⁇ m and had a homogeneous composition.
  • a powder was prepared from the above solutions in the same manner as in Example 54 except that the firing temperature is 350° C. This powder was also yellowish.
  • the powder was measured by X-ray diffraction to show that 80% of the powder was amorphous or that it was substantially amorphous. Further, the powder was analyzed for a composition to show that the atomic ratio of In, In/(In+Zn), was 0.85. This powder comes under the electrically conductive material III.
  • the above powder was measured for a volume solid resistivity to show 4 ⁇ cm.
  • the powder still showed a volume solid resistivity of 6 ⁇ cm or showed almost no change after a 1,000 hours' test on humidity resistance under the conditions of 40° C. and 90% RH. This shows that the powder was excellent in humidity resistance.
  • the powder was also analyzed with SEM and XMA to show that it had an average particle diameter of 0.15 ⁇ m and had a homogeneous composition.
  • a powder was prepared from the above solutions in the same manner as in Example 54. This powder was also yellowish.
  • the powder was measured by X-ray diffraction to show that 90% of the powder was amorphous or that it was substantially amorphous. Further, the powder was analyzed for a composition to show that the atomic ratio of In, In/(In+Zn), was 0.67 and the atomic ratio of tin, Sn/(In+Zn+Sn) was 0.09. This powder comes under the electrically conductive material IV.
  • the above powder was measured for a volume solid resistivity to show 4 ⁇ cm.
  • the powder still showed a volume solid resistivity of 6 ⁇ cm or showed almost no change after a 1,000 hours' test on humidity resistance under the conditions of 40° C. and 90% RH. This shows that the powder was excellent in humidity resistance.
  • the powder was also analyzed with SEM and KMA to show that it had an average particle diameter of 0.17 ⁇ m and had a homogeneous composition.
  • a powder was prepared from the above solutions in the same manner as in Example 55. This powder was also yellowish.
  • the powder was measured by X-ray diffraction to show that 80% of the powder was amorphous or that it was substantially amorphous. Further, the powder was analyzed for a composition to show that the atomic ratio of In, In/(In+Zn), was 0.60. This powder comes under the electrically conductive material III.
  • the above powder was measured for a volume solid resistivity to show 20 ⁇ cm.
  • the powder still showed a volume solid resistivity of 22 ⁇ cm or showed almost no change after a 1,000 hours' test on humidity resistance under the conditions of 60° C. and 65% RH. This shows that the powder was excellent in humidity resistance.
  • the powder was also analyzed with SEM and XMA to show that it had an average particle diameter of 0.19 ⁇ m and had a homogeneous composition.
  • the solvent was removed from the above solution under reduced pressure at 80° C., and the remainder was fired at 400° C. for 1 hour to carry out the thermal decomposition thereof. Then, the resultant powder was reduction-treated under vacuum at 200° C. for 2 hours to give a yellowish powder.
  • the powder was measured by X-ray diffraction to show that 80% of the powder was amorphous or that it was substantially amorphous. Further, the powder was analyzed for a composition to show that the atomic ratio of In, In/(In+Zn), was 0.70. This powder comes under the electrically conductive material III.
  • the above powder was measured for a volume solid resistivity to show 7 ⁇ cm.
  • the powder still showed a volume solid resistivity of 8 ⁇ cm or showed almost no change after a 1,000 hours' test on humidity resistance under the conditions of 60° C. and 95% RH, which shows that the powder was excellent in humidity resistance.
  • the powder was also analyzed with SEM and XMA to show that it had an average particle diameter of 0.15 ⁇ m and had a homogeneous composition.
  • the transparent electrically conductive layers (transparent electrically conductive layer I and transparent electrically conductive layer II) of the present invention are transparent electrically conductive film which have practically sufficient electrical conductivity and light transmittance, and which are excellent in resistance to moist heat and etching properties. According to the present invention, therefore, there can be provided transparent electrically conductive films which are improved in durability and which can be easily shaped into desired forms by an etching method.
  • the electrically conductive transparent substrates (electrically conductive transparent film and electrically conductive transparent glass) of the present invention are those which utilize the above transparent electrically conductive films, and since these transparent electrically conductive films have the above properties, they are suitable base materials for forming transparent electrodes, by an etching method, in various fields such as a transparent electrode for a liquid crystal display device, a transparent electrode for an electroluminescence device and a transparent electrode for a solar cell, or a film for the prevention of electrostatic charge or a heater for deicing on window glass.
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KR100306565B1 (ko) 2001-11-30
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DE69328197T2 (de) 2000-08-17
WO1994013851A1 (en) 1994-06-23
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KR950704533A (ko) 1995-11-20
EP0677593B1 (de) 2000-03-22

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